Aminoplast-anchored ultraviolet light stabilizers

ABSTRACT

Novel aminoplast anchored UV stabilizers are provided. Compared to unanchored stabilizers, the anchored stabilizers disclosed herein have increased compatibility with coating resins and have reduced volatility due to higher molecular weights resulting from anchoring. A process for preparing the anchored stabilizers by the reaction of unanchored stabilizers with alkoxymethylated aminoplasts in a sulfuric acid medium is also provided. The unanchored stabilizers include 2-(2-hydroxyaryl)benzotriazoles, 2-hydroxybenzophenones, 2-(2-hydroxyaryl)-4,6-diaryl-1,3,5-triazines, salicylic acid derivatives, 2-hydroxyoxanilides, and blocked derivatives thereof as well as mixtures of two or more stabilizers. The aminoplasts include alkoxymethylated derivatives of glycolurils, melamines, and benzoguanamines.

This is a divisional of co-pending application Ser. No. 07/998,099,filed Dec. 29, 1992.

FIELD OF THE INVENTION

This invention relates to the preparation and use of novelaminoplast-anchored phenolic ultraviolet light stabilizers.

BACKGROUND OF THE INVENTION

Stabilization of polymers by incorporation of ultraviolet lightstabilizers in polymer films, coatings, fibers, and molded articles toprovide protection against the degrading action of light, moisture, oroxygen has been an active area of work in recent years. However,deficiencies such as volatility and generally poor retention of existingstabilizers within a polymer matrix still remain largely unsolved. Forexample, attempts to reduce volatility by using higher molecular weightoligomers and polymers have generally resulted in a decreased retentionof the stabilizer due to incompatibility. Extractibility and migrationof the stabilizer to the surface and eventually loss as a result ofincompatibility or low molecular weight are still serious problemsplaguing the plastics industry.

Limited attempts to increase the molecular weight of the stabilizerwithout introducing incompatibility by using anchor groups have beenmade in the past without great success. Among the anchor groups used forsupporting stabilizers, triazines have received some attention. U.S.Pat. No. 4,319,016 describes an ultraviolet absorbing material which isthe reaction product of (a) a hydroxyphenyl ultraviolet light absorbingcompound, (b) formaldehyde, and (c) an amino-group containing compound,such as melamine. It is stated therein that if the hydroxyphenylcompound is present in amounts greater than 0.5 mole per mole ofmelamine, the amount of unreacted hydroxyphenyl compound frequentlyincreases and the compatibility of the resulting compound with a resinor solvent tends to be reduced. The reaction product obtained by themethod described therein is not described in the patent.

U.S. Pat. Nos. 3,535,318; 3,595,602; 4,418,000; 4,418,001; and4,418,002; and Japense Patent No. 01-287160 describe reaction productsobtained by reacting hydroxy group-containing ultraviolet absorbers withalkoxymethyl-group containing aminoplasts. The attachment of theultraviolet absorbing group of the aminoplast anchor, however, is alwaysthrough a weak carbon-oxygen bond between the bridging methylene groupof the aminoplast and the hydroxy group of the ultraviolet lightabsorbing component.

U.S. Pat. Nos. 3,316,208; 4,197,392; and 4,913,974; and Canadian PatentNo. 1,065,991 describe acid curable compositions containing ultravioletlight absorbers and alkoxymethyl group-containing aminoplast. Despitethe presence of acids, there is no suggestion in these references of anyreaction between the absorber component and the aminoplast component ofsaid curable compositions.

U.S. Pat. Nos. 4,612,358; 4,652,656; and 3,399,173; Japense Patent No.63-205334; and a review article in "Caoutchoucs et Plastiques", No. 575,November 1977 describe ultraviolet light absorbing polymerizablemonomers and polymers thereof. An article in "Polymer Degradation andStability," Vol. 25, pages 121-141 (1989) entitled "New Developments inPolymer Stabilization" describes the effects of molecular weight ofstabilizers on performance. U.S. Pat. No. 4,355,071 describes clearcoat/color coat finishes in which stabilizers are able to migrate acrossthe interface. An article in Journal of Polymer Science, PolymerLetters, Volume 15, Number 11, pages 675 to 677 (1977) and U.S. Pat.Nos. 4,612,358 and 4,652,656 disclose the use of 95 to 98% sulfuric acidin the preparation of polymerizable, benzophenone and benzotriazole typestabilizers. U.S. Pat. No. 4,233,430 similarly discloses the use ofsulfuric acid in the preparation of related polymers.

The object of this invention is to provide novel aminoplast-anchoredblocked and unblocked phenolic stabilizers.

Another object of this invention is to provide a process for thepreparation of the novel stabilizers of the invention.

It is yet another object of this invention to provide curablecompositions containing the novel stabilizers of the invention and alsoprovide stabilized cured compositions obtained by curing said curablecompositions.

It is yet another object of this invention to provide an improved methodof stabilizing polymers wherein the improvement comprises adding to saidpolymers the novel stabilizers of the invention.

SUMMARY OF THE INVENTION

This invention is a novel composition of matter comprising blocked orunblocked, monomeric and oligomeric aminoplast-anchored phenolicultraviolet light stabilizer having at least 0.5 mole of phenolicstabilizer groups per mole of aminoplast anchor.

This invention is also a process for preparing the novel stabilizers ofthe invention.

This invention is also a curable composition containing the novelstabilizers of the invention.

This invention is also a cured composition containing the novelstabilizers of the invention.

This invention is also an improved method of stabilizing polymerswherein the improvement comprises adding to said polymers the novelstabilizers of the invention.

The advantages of the anchored stabilizers of this invention over theirunanchored precursors include generally higher compatibility withpolymers and resins, and generally lower volatility due to highermolecular weights.

DETAILED DESCRIPTION OF THE INVENTION

The novel composition of this invention is an amino resin anchormolecule having pendant on it one or more phenolic stabilizer groups.The broad discovery of this invention is that chemically combining aminoresins and phenolic stabilizers into a single compound or oligomeryields a composition of matter that unexpectedly retains the stabilizingeffect of the phenolic stabilizer, permits combinations of stabilizersat the molecular level, and gains advantageous properties from the aminoresins such as enhanced compatibility and reduced volatility.

For example, the gain in molecular weight by the chemical combination ofthe stabilizer and amino resin generally makes the novel compositionsless volatile in polymeric compositions, thereby minimizing loss andtoxicity. The gain in solubility in resins generally makes thecompositions more compatible with the matrix, thereby minimizingextractibility and loss.

The present invention provides a wide variety anchored stabilizersbecause of the ability to change any of the following variables:

1. The type of amino resin anchors.

2. The type of stabilizer reactant(s).

3. Degree of reaction of (1.) and (2.) (extent of substitution).

The following sections of this Detailed Description will illustrateuseful types of amino resins for formation of the novel compounds of theinvention. By way of example, specific use of the following amino resintypes is set forth below:

1. glycoluril type resins

2. melamine type resins

3. guanamine type resins

The following sections will also illustrate useful types of phenolicstabilizers for formation of the novel compounds of the invention. Byway of example, specific use of the following chemical classes ofstabilizers is set forth below:

1. benzotriazoles

2. benzophenones

3. aryltriazines

4. salicylic acid derivatives

5. oxanilides

It should specifically be noted that more than one type of stabilizer(viz., a mixture of stabilizers) may be placed on an amino resin anchormolecule. This provides a novel product with a wide spectral responsehaving particular utility for ultraviolet and actinic light induceddegradation.

The following sections will also illustrate the variety of novelcompounds resulting from the degree of reaction between the amino resinanchor and the stabilizer.

The amino resin anchor may be fully or partially reacted with thestabilizer, creating three categories of novel compounds as follows:

1. Amino resin/stabilizer compounds wherein the stabilizer is on theaverage reacted with substantially all of the available reactive siteson the amino resin. This results in a novel compound having a highdegree of stabilizer activity and reduced volatility.

2. Amino resin/stabilizer compounds wherein the stabilizer is on theaverage reacted with all but one of the available reactive sites on theamino resin. This results in a novel compound which can chemicallycombine with plastics which are known to react with amino resins to givea pendant group with stabilizer functionality.

3. Amino resin/stabilizer compounds wherein the stabilizer is on theaverage reacted so as to leave two or more available reactive sites onthe amino resin. This results in a novel compound which can chemicallyact as a crosslinking agent. Such novel crosslinking agents also act asstabilizers.

The word "stabilizer" is used herein to mean a group derived from aphenolic compound that has known utility to prevent degradation byenvironmental forces, inclusive of ultraviolet light, actinic radiation,oxidation, moisture, atmospheric pollutants, and combinations thereof.

The novel aminoplast-anchored ultraviolet (UV) stabilizers of thisinvention are monomeric or oligomeric aminoplasts having more than 0.5mole of pendently attached phenolic light stabilizer groups per mole ofaminoplast. The phenolic light stabilizer moiety may be any conventionalUV stabilizer, such as one selected from the group consisting of:

(1) 2-(2-hydroxyaryl)benzotriazoles,

(2) 2-hydroxybenzophenones,

(3) 2-(2-hydroxyaryl)-4,6-diaryl-1,3,5-triazines,

(4) salicylic acid derivatives,

(5) 2-hydroxyoxanilides,

(6) blocked derivatives of (1) to (5), wherein the phenolic OH group isblocked with a suitable blocking group, and

(7) mixtures of (1) to (6).

The novel aminoplast-anchored phenolic UV stabilizers of the inventionhave a monomeric or oligomeric aminoplast nucleus which has more than0.5 mole of phenolic UV stabilizer groups per mole of aminoplastpendently attached thereto with methylene bridges. Generically, thenovel stabilizers of this invention may be represented by the followingformula:

    (UV Stabilizer --CH.sub.2).sub.n --A

wherein

A is a monomeric or oligomeric aminoplast anchor molecule serving as anucleus for supporting the pendently attached phenolic UV stabilizergroups; and

n is a number having an average minimum value greater than 0.5 and amaximum value equal to the number of stabilizer-reactive groups presenton the aminoplast anchor.

The stabilizer-reactive group in the aminoplast anchor molecule istypically an alkoxymethyl group, but other reactive groups, such ashydroxy, acyloxy, halo, mercapto, sulfonyl, sulfonate, sulfate,phosphate, dialkylsulfonium, trialkylammonium, and the like may also beused.

The unblocked or hydroxyl-blocked novel aminoplast anchored phenolicstabilizers of the invention may also be represented by the followingformula: ##STR1## wherein A is an m functional monomeric or oligomericaminoplast anchor molecule to which n phenolic rings are attachedthrough n methylene bridges, said bridges replacing R², R³, R⁴, or R⁵groups on said phenolic rings;

R¹ is a group which, together with the phenolic ring, comprises aphenolic UV stabilizer;

R², R³, R⁴, and R⁵ are substituents selected from the group consistingof hydrogen, alkyl, aryl, aralkyl, hydroxy, alkoxy, and oxygenated alkylgroups; and

R⁶ is hydrogen or a blocking group selected from the group consisting ofalkyl, acyl, aminocarbonyl, and silyl groups.

By m functional aminoplast, it is meant that there are m reactive groupson the aminoplast anchor molecule each of which can potentially reactwith a light stabilizer group to form the aminoplast-anchored lightstabilzers of this invention.

AMINOPLAST ANCHORS

The aminoplast anchor molecules of this invention are aminoplastcrosslinkers commonly used in coatings, moldings, and adhesives. Theterm "aminoplast" is defined herein as a class of resins which may beprepared by the reaction of an amino group-containing compound and analdehyde.

The reaction product of amino group-containing compounds and aldehyde isoften reacted further with an alcohol to produce partially or fullyalkylated derivatives. These derivatives are included in the"aminoplast" definition given above. The term "aminoplast" as used inthe context of this invention comprises typically a polyfunctional aminoresin, and may be monomeric or oligomeric. For example, in thepreparation of aminoplasts from amino group-containing compounds andaldehydes and subsequent alkylation, dimeric and oligomeric productsresulting from self-condensation reaction are often obtained. Theseoligomeric self-condensation products are included in the "aminoplast"definition given above.

By way of example, the aminoplast anchors A of this invention includethe groups represented by the following formulae (1)-(17): ##STR2##wherein R⁷ and R⁸ are independently, hydrogen, alkyl or aryl groups of 1to 20 carbon atoms; ##STR3## wherein R¹⁰ is an aliphatic orcycloaliphatic alkyl group, of 1 to 20 carbon atoms, such as methyl,ethyl, butyl, cyclohexyl and the like; or

R¹⁰ is an aromatic group, of 1 to 20 carbon atoms, such as phenyl,tolyl, naphthyl, and the like; or

R¹⁰ is an aralkyl group, of 1 to 20 carbon atoms, such as benzyl, cumyl,and the like; ##STR4## wherein R is an alkylene or an arylene group of 1to 20 carbon atoms; ##STR5## (10) polyfunctional carbamates; (11)polyfunctional amides;

(12) hydantoins;

(13) dialkoxyethylene ureas;

(14) dihydroxyethylene urea represented by the formula: ##STR6## (15)homopolymers and copolymers containing carbamate units of the formula:##STR7## wherein R is hydrogen or alkyl, and m is at least 1; (16)oligomeric derivatives thereof; and

(17) mixtures of any of (1) through (16).

The aminoplast may have, as a substituent, a hydrogen, an alkyl or anaryl group of 1 to about 20 carbon atoms, or a stabilizer reactive groupsuch as --CH₂ OH and --CH₂ OR⁹ wherein R⁹ is an alkyl group of 1 toabout 20 carbon atoms or an aminoplast group-containing oligomeric groupprovided that the total number of stabilizer reactive groups per eachaminoplast anchor is at least 1, and preferably more than 1.

The preferred aminoplast anchors of this invention are substantiallyfully etherified, substantially fully methylolated, substantiallymonomeric aminoplast crosslinkers commonly used in the coatingsindustry. They are characterized by having at least two, and preferablymore than two, stabilizer-reactive groups per anchor molecule.

The most preferred aminoplast anchors of the invention are selected froma group consisting of substantially fully etherified, substantiallyfully methylolated, substantially monomeric glycoluril, melamine,benzoguanamine, cyclohexanecarboguanamine, urea, and mixtures thereof.

In addition to the substantially fully etherified, substantiallymonomeric amine-aldehyde aminoplast anchors described above, thenon-etherified or partially etherified, substantially fully methylolatedor partially methylolated monomeric and oligomeric aminoplasts are alsousable in the composition of this invention.

Aminoplast anchors which contain very few alkoxymethyl groups generallyhave low solubilities due to the high N-H levels, and therefore are lesspreferred.

The most preferred aminoplast anchors are exemplified in greater detailbelow.

GLYCOLURIL ANCHORS

The most preferred glycoluril anchors of this invention areN-substituted glycolurils represented by the formula: ##STR8## whereinat least two of the R groups are selected from the group consisting ofmethoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, pentoxymethyl,hexoxymethyl, heptoxymethyl, octoxymethyl, nonoxymethyl, decoxymethyland mixtures thereof, and the remaining R groups are selected fromhydrogen, alkyl, hydroxymethyl, and glycoluril group-containingoligomeric moieties.

While it is preferable to have a multiplicity of alkoxymethyl groups pereach glycoluril anchor molecule, under ordinary circumstances it is notnecessary to obtain, for example, a pure tetra-substituted monomericaminoplast such as N,N',N",N'"-tetraalkoxymethylglycoluril representedby formula: ##STR9## wherein R is an alkyl group of 1 to about 20 carbonatoms. The glycoluril may contain monomeric as well as oligomericcomponents.

The monomeric tetraalkoxyglycolurils themselves are not considered to beresinous materials since they are, as individual entities, non-polymericcompounds. They are considered, however, to be potential resin-formingcompounds when subjected to heat, and particularly when subjected toheat under acidic conditions. As a result of the described resin-formingability, the substantially monomeric glycoluril aminoplasts of thisinvention may produce, during the course of the reaction, varyingamounts of oligomeric components such as dimers, trimers, and tetramers.The presence of varying amounts of these oligomeric forms is permissibleand, indeed beneficial, particularly in cases where higher molecularweight and lower volatility products are desired as in the case of mostapplications in which the products are used as stabilizers against thedegrading action of UV light. An example of glycoluril anchors of thisinvention is POWDERLINK® 1174 powder aminoplast resin, a product ofAmerican Cyanamid Company, Wayne, N.J. It has the following formula andproperties:

    ______________________________________                                         ##STR10##                                                                

    ______________________________________                                        Non Volatiles, minimum                                                                            98                                                        (% by weight)                                                                 Appearance          White to pale yellow                                                          granulated flakes                                         Melting Point (°C.)                                                                        90-110° C.                                         Average Molecular Weight                                                                          350                                                       Equivalent Weight   90-125                                                    ______________________________________                                    

Another example of a glycoluril anchor usable in this invention isCYMEL® 1170 fully butylated glycoluril resin, a product of AmericanCyanamid Company, Wayne, N.J., having the following properties:

    ______________________________________                                        Non Volatiles, minimum 95                                                     (% by weight)                                                                 Appearance             Clear liquid                                           Color, Maximum (Gardner 1963)                                                                        3                                                      Viscosity (Gardner-Holt, 25° C.)                                                              X--Z.sub.2                                             Average Molecular Weight                                                                             550                                                    Equivalent Weight      150-230                                                Methylol Content       Very low                                               ______________________________________                                    

UREA ANCHORS

An example of a urea usable in this invention is BEETLE® 80 butylatedurea-formaldehyde resin, a product of American Cyanamid Company, Wayne,N.J., having the following properties:

    ______________________________________                                        Appearance             Clear Liquid                                           Color, Maximum (Gardner 1963)                                                                        1                                                      Non-Volatiles (Weight %)*                                                                            96 ± 2                                              Viscosity (Gardner-Holt, 25° C.)                                                              X--Z.sub.3                                             Solvent Tolerance (ASTM                                                                              >500                                                   D1198-55)                                                                     ______________________________________                                         *Foil Method (45° C./45 min.)                                     

MELAMINE ANCHORS

The melamine-based aminoplast anchors of this invention are well knownper se, and have been used extensively as effective crosslinkers incoatings.

Unlike the tetrafunctional glycolurils, alkoxymethylmelaminefunctionality can be a maximum of six in a stabilizingly effective rangeof 1 to 6 stabilizer reactive alkoxymethyl groups per each melaminemolecule.

Like the glycolurils, in addition to monomers, alkoxymethyl melaminescan contain dimers, trimers, tetramers, and higher oligomers, each givencombination of monomers and oligomers being preferred for a givenapplication. For example, the lower viscosity monomerrich compositionsare preferred for solvent-based high solids coatings.

An example of a substantially fully etherified, substantially fullymethylolated, substantially monomeric melamines usable in this inventionis CYMEL® 303 melamine crosslinking agent, a product of AmericanCyanamid Company, Wayne, N.J., which has the following formula andproperties:

    ______________________________________                                         ##STR11##                                                                

    ______________________________________                                        Non-Volatiles (% by weight)*                                                                            98                                                  Color, maximum (Gardner 1963)                                                                           1                                                   Viscosity (Gardner-Holt, 25° C.)                                                                 X-Z.sub.2                                           Free Formaldehyde, maximum                                                                              0.5                                                 (weight 5)                                                                    Degree of Polymerization  1.75                                                ______________________________________                                         *Foil Method (45° C./45 min.)                                     

Another example of a substantially fully etherified, substantially fullymethylolated, substantially monomeric melamine is CYMEL® 1168 aminoplastresin, a product of American Cyanamid Company, Wayne, N.J. The alkylgroup in CYMEL® 1168 consists essentially of a mixture of methyl andisobutyl groups.

It has the following formula (wherein R=methyl or isobutyl) andproperties:

    ______________________________________                                         ##STR12##                                                                

    ______________________________________                                        Non-Volatiles (% by weight)*                                                                           98                                                   Color, maximum (Gardner 1963)                                                                          1                                                    Free Formaldehyde, maximum                                                                             0.5                                                  (weight %)                                                                    Viscosity (Gardner-Holt, 25° C.)                                                                X-Z.sub.2                                            Equivalent weight        150-230                                              ______________________________________                                         *Foil Method (45° C./45 min.)                                     

An example of substantially methylolated, partially etherified,substantially oligomeric melamine is CYMEL® 370 crosslinking agent, aproduct of American Cyanamid Company, Wayne, N.J. It has the followingproperties:

    ______________________________________                                        Non-Volatiles (% by weight)*                                                                          88 ± 2                                             Solvent                 Isobutanol                                            Viscosity (Gardner-Holt, 25° C.)                                                               Z.sub.2 --Z.sub.4                                     Color, maximum (Gardner 1963)                                                                         1                                                     Equivalent weight       225-325                                               ______________________________________                                         *Foil Method (45° C./45 min.)                                     

GUANAMINE ANCHORS

As in melamines, the partially or fully methylolated or etherified alkyland aryl guanamine aminoplasts, both in their monomeric and oligomericforms, are usable as anchors in this invention, with the selectiondepending on the particular application or the properties desired in theproduct.

Benzoguanamine, cyclohexylcarboguanamine and acetoguanamine aminoplastsare especially preferred as anchors in this invention. Thebenzoguanamines are represented by the formula: ##STR13## wherein R isan alkyl group of 1 to about 20 carbon atoms, or a mixture thereof. Anexample of a benzoguanamine-based anchor is CYMEL® 1123 resin asdescribed above, wherein R is a mixture of methyl and ethyl groups.

The acetoguanamine-based anchors are represented by the formula:##STR14## wherein R is an alkyl group of 1 to about 20 carbon atoms, ora mixture thereof.

The cyclohexylcarboguanamine-based anchors are represented by theformula: ##STR15## wherein R is an alkyl group of 1 to about 20 carbonatoms, or a mixture thereof.

It is evident from the above, that a person skilled in the art, inselecting suitable anchors for a particular application, may choose amixture thereof which imparts a balance of properties desired for thatparticular application.

PENDENT PHENOLIC STABILIZERS

The phenolic stabilizers useful as reactants may be in the free phenolicform (R=H, infra) or it may be in the blocked form (R=a group other thanhydrogen, such as a acetyl group, or a trimethylsilyl group, or an ethylgroup, infra).

The blocked and unblocked phenols usable in the preparation of the novelaminoplast anchored stabilizers of the invention are represented by theformula: ##STR16## wherein R¹ is selected from the group consisting of:##STR17## wherein each of R¹¹ through R¹⁴ is independently selected fromthe group consisting of alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20carbon atoms, aralkyl of 7 to 20 carbon atoms, hydrogen, chloro, bromo,cyano, and nitro group; ##STR18## wherein each of R¹⁵ and R¹⁶ isindependently selected from the group consisting of alkyl of 1 to 20carbon atoms, aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 20 carbonatoms, hydrogen, chloro, bromo, cyano, nitro, and hydroxy groups;##STR19## wherein Y and Z are the same or different aromatic carbocyclicradicals; and

wherein each of R¹⁷ through R²² is independently selected from the groupconsisting of alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbonatoms, hydrogen, chloro, bromo, cyano, carboxy, and nitro groups;

(m) carboxylic acid group or amides and esters thereof; ##STR20##wherein each of R²³ and R²⁴ is the same or different, and isindependently selected from the group consisting of alkyl of 1 to 20carbon atoms, aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 20 carbonatoms, hydrogen, chloro, bromo, cyano, and nitro groups; and

(o) mixtures thereof; and

wherein

R² is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms; and

wherein

R³ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, aralkyl of 7 to 20 carbon atoms, and alkyl of 1 to 20carbon atoms which is interrupted, substituted, or interrupted andsubstituted by one or more oxygen, carbonyl, or carboxy groups; and

wherein

R⁴ is selected from the group consisting of hydrogen, hydroxy, alkyl of1 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 20carbon atoms, and alkyl of 1 to 20 carbon atoms which is interrupted,substituted, or interrupted and substituted by one or more oxygen,carbonyl, or carboxy groups;

wherein

R⁵ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms; and

wherein

R is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, acyl of 1 to 20 carbon atoms, alkylaminocarbonyl of 1 to20 carbon atoms, arylaminocarbonyl of 6 to 20 carbon atoms, andtrisubstituted silyl groups.

The unblocked stabilizers are generally more active than theircorresponding blocked counterparts as ultraviolet light stabilizersbecause of the well recognized interaction of the hydrogen atom on thehydroxy group of the stabilizer with a neighboring group such as acarbonyl, an ester, or an sp² hybridized nitrogen atom.

The blocked stabilizers, however, are capable of deblocking either underprocessing conditions or under use conditions thereby producing thegenerally more active unblocked forms.

Deblocking may be effected by the action of acids, bases, heat,moisture, or oxidative processes initiated by free radicals oratmospheric oxygen.

The phenolic stabilizers usable in this invention are well known in theart and include a variety of UV absorbers.

Various classes of phenolic UV stabilizers suitable for use in thepreparation of the aminoplast anchored novel stabilizers of theinvention are exemplified in greater detail below:

A. BENZOTRIAZOLES

The benzotriazole type UV stabilizers usable in the preparation of thestabilizers of the invention are a widely known class of UV absorbers,and are represented by the formula: ##STR21## wherein each of R¹¹through R¹⁴ is independently selected from the group consisting of alkylof 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, aralkyl of 7 to20 carbon atoms, hydrogen, chloro, bromo, cyano, and nitro groups;

wherein

R² is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms;

wherein

R³ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, aralkyl of 7 to 20 carbon atoms, and alkyl of 1 to 20carbon atoms which is interrupted, substituted, or interrupted andsubstituted by one or more oxygen, carbonyl, or carboxy groups;

wherein

R⁴ is selected from the group consisting of hydrogen, hydroxy, alkyl of1 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 20carbon atoms, and alkyl of 1 to 20 carbon atoms which is interrupted,substituted, or interrupted and substituted by one or more oxygen,carbonyl, or carboxy groups;

wherein

R⁵ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms; and

wherein

R is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, acyl of 1 to 20 carbon atoms, alkylaminocarbonyl of 1 to20 carbon atoms, arylaminocarbonyl of 6 to 20 carbon atoms, andtrisubstituted silyl groups.

The preferred benzotriazole type stabilizers usable as starting materialin the preparation of the aminoplast-anchored stabilizers of theinvention are represented by the formulae: ##STR22## B. BENZOPHENONES

The benzophenone type UV stabilizers usable in the preparation of thestabilizers of the invention are represented by the formula: ##STR23##wherein each of R¹⁵ and R¹⁶ is independently selected from the groupconsisting of alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbonatoms, hydrogen, chloro, bromo, cyano, nitro, and hydroxy groups;

wherein

R² is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms;

wherein

R³ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, aralkyl of 7 to 20 carbon atoms, and alkyl which isinterrupted, substituted or interrupted and substituted by one or moreoxygen, carbonyl, or carboxy groups;

wherein

R⁴ is selected from the group consisting of hydrogen, hydroxy, alkyl of1 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 20carbon atoms, and alkyl which is interrupted, substituted, orinterrupted and substituted by one or more oxygen, carbonyl, or carboxygroups;

wherein

R⁵ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms; and

wherein

R is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, acyl of 1 to 20 carbon atoms, alkylaminocarbonyl of 1 to20 carbon atoms, arylaminocarbonyl of 6 to 20 carbon atoms, andtrisubstituted silyl groups.

The preferred benzophenone type stabilizers are represented by theformulae, all products of the American Cyanamid Company, Wayne, N.J.:##STR24## C. ARYLTRIAZINES

The aryltriazine type UV absorbers usable as starting materials arerepresented by the formula: ##STR25## wherein Y and Z are the same ordifferent aromatic carbocyclic radicals;

wherein

each of R¹⁷ through R²² is the same or different and is independentlyselected from the group consisting of alkyl of 1 to 20 carbon atoms,alkoxy of 1 to 20 carbon atoms, hydrogen, chloro, bromo, cyano, carboxy,and nitro groups;

wherein

R² is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms;

wherein

R³ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, aralkyl of 7 to 20 carbon atoms, and alkyl which isinterrupted, substituted, or interrupted and substituted by one or moreoxygen, carbonyl, or carboxy groups;

wherein

R⁴ is selected from the group consisting of hydrogen, hydroxy, alkyl of1 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 20carbon atoms, and alkyl which is interrupted, substituted, orinterrupted and substituted by one or more oxygen, carbonyl, or carboxygroups;

wherein

R⁵ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms; and

wherein

R is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, acyl of 1 to 20 carbon atoms, alkylaminocarbonyl of 1 to20 carbon atoms, arylaminocarbonyl of 6 to 20 carbon atoms, andtrisubstituted silyl groups.

The preferred aryltriazine UV stabilizers usable as starting materialsin the preparation of the anchored stabilizers of the invention arerepresented by the formula: ##STR26## wherein each of R¹⁷ through R²² isindependently selected from the group consisting of alkyl of 1 to 20carbon atoms, alkoxy of 1 to 20 carbon atoms, hydrogen, chloro, bromo,cyano, and nitro groups; and

wherein R and R⁴ have the same meaning as above.

An example of the preferred aryltriazine type UV stabilizer isrepresented by the formula: ##STR27## D. SALICYLIC ACID DERIVATIVES

The salicylic acid type stabilizers suitable for use as startingmaterials are represented by the formula: ##STR28## wherein X isselected from the group consisting of morpholino, piperidino,pyrrolidino groups, OR³⁰, and NR³¹ R³² groups;

wherein R³⁰ is selected from the group consisting of hydrogen, silyl,alkyl of 1 to 20 carbon atoms, aryl of 1 to 20 carbon atoms, aralkyl of7 to 20 carbon atoms, and mixtures thereof; and

wherein each of R³¹ and R³² is the same or different and is selectedfrom the group consisting of hydrogen, alkyl of 1 to 20 carbon atoms,aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms;

wherein

R², R³, R⁴, and R⁵ are the same or different and each is selected fromthe group consisting of hydrogen, alkyl of 1 to 20 carbon atoms, andaralkyl of 7 to 20 carbon atoms; and

wherein

R is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, acyl of 1 to 20 carbon atoms, alkylaminocarbonyl of 1 to20 carbon atoms, arylaminocarbonyl of 6 to 20 carbon atoms, andtrisubstituted silyl groups.

The preferred class of salicylic acid or its esters is represented bythe formula: ##STR29## wherein R³⁰ is selected from the group consistingof hydrogen, alkyl of 1 to 20 carbon atoms, aryl of 1 to 20 carbonatoms, aralkyl of 7 to 20 carbon atoms, and mixtures thereof.

E. OXANILIDES

The oxanilide type stabilizers suitable for use as starting materials inthe preparation of the aminoplast anchored stabilizers of the inventionare represented by the formula: ##STR30## wherein each of R²³ and R²⁴ isthe same or different, and is independently selected from the groupconsisting of alkyl of 1 to 20 carbon atoms, aralkyl of 7 to 20 carbonatoms, alkoxy of 1 to 20 carbon atoms, hydrogen, chloro, bromo, cyano,and nitro groups;

wherein

R² is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms;

wherein

R³ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, aralkyl of 7 to 20 carbon atoms, and alkyl which isinterrupted, substituted, or interrupted and substituted by one or moreoxygen, carbonyl, or carboxy groups;

wherein

R⁴ is selected from the group consisting of hydrogen, hydroxy, alkyl of1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, aralkyl of 7 to 20carbon atoms, and alkyl which is interrupted, substituted, orinterrupted and substituted by one or more oxygen, carbonyl, and carboxygroups;

wherein

R⁵ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms; and aralkyl of 7 to 20 carbon atoms; and

wherein

R is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, acyl of 1 to 20 carbon atoms, alkylaminocarbonyl of 1 to20 carbon atoms, arylaminocarbonyl of 6 to 20 carbon atoms, andtrisubstituted silyl groups.

The preferred oxanilide is SANDOVUR® 3206 light stabilizer, a product ofSandoz Corporation, Basel, Switzerland, represented by the formula:##STR31## ANCHORED PRODUCTS AMINOPLAST ANCHORED UNBLOCKED STABILIZERS

The unblocked aminoplast anchored phenolic UV stabilizers of theinvention are represented by the formula: ##STR32## wherein A is a an mfunctional aminoplast anchor molecule to which n phenol rings areattached through n methylene bridges, said bridges replacing R³, R⁴, orR⁵ groups on said phenol rings, which aminoplast anchor molecule isselected from the group consisting of: ##STR33## wherein R⁷ and R⁸ areindependently selected from the group consisting of hydrogen, alkyl of 1to 20 carbon atoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20carbon atoms; and wherein R⁹ is a linear or branched alkyl group of 1 tocarbon atoms; ##STR34## wherein R¹⁰ is selected from the groupconsisting of alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbonatoms, and aralkyl of 7 to 20 carbon atoms; and wherein R⁹ is a linearor branched alkyl group of 1 to 20 carbon atoms; ##STR35## wherein R⁹ isa linear or branched alkyl group of 1 to 20 carbon atoms; ##STR36##wherein R⁹ is a linear or branched alkyl group of 1 to 20 carbon atoms;##STR37## wherein R⁹ is a linear or branched alkyl group of 1 to 20carbon atoms; ##STR38## wherein R⁹ is a linear or branched alkyl groupof 1 to 20 carbon atoms; ##STR39## wherein R⁹ is a linear or branchedalkyl group of 1 to 20 carbon atoms

(h) oligomeric aminoplast anchor molecules derived from the self- orcross-condensation of any of (a) through (g) or mixtures thereof;

(i) mixtures of any of (a) through (h) ;

wherein m is at least 1; and wherein n is more than 0.5; and

wherein R¹ is selected from the group consisting of: ##STR40## whereineach of R¹¹ through R¹⁴ is independently selected from the groupconsisting of alkyl of 1 to 20 carbon atoms, alkoxy or 1 to 20 carbonatoms, aralkyl of 7 to 20 carbon atoms, hydrogen, chloro, bromo, cyano,and nitro groups; ##STR41## wherein each of R¹⁵ and R¹⁶ is independentlyselected from the group consisting of alkyl of 1 to 20 carbon atoms,aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms,hydrogen, chloro, bromo, cyano, nitro and hydroxy groups; ##STR42##wherein each of R¹⁷ through R²² is independently selected from the groupconsisting of alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbonatoms, hydrogen, chloro, bromo, cyano, and nitro groups;

(m) carboxylic group or amides and esters thereof; ##STR43## whereineach of R²³ and R²⁴ is independently selected from the group consistingof alkyl of 1 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms,alkoxy of 1 to 20 carbon atoms, hydrogen, chloro, bromo, cyano, andnitro groups; and

(o) mixtures thereof; and

wherein

R² is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms;

wherein

R³ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, aralkyl of 7 to 20 carbon atoms, and alkyl of 1 to 20carbon atoms which is interrupted, substituted, or interrupted andsubstituted by one or more oxygen, carbonyl, or carboxy groups;

wherein

R⁴ is selected from the group consisting of hydrogen, hydroxy, alkyl of1 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, and alkyl of 1 to20 carbon atoms which is interrupted, substituted, or interrupted andsubstituted by one or more oxygen, carbonyl, and carboxy groups; and

wherein

R⁵ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms.

The stabilizer to aminoplast ratio in the anchored stabilizers of theinvention is greater than 0.5:1, preferably the ratio is greater than1:1, and most preferably the ratio is greater than 2:1.

AMINOPLAST ANCHORED BENZOTRIAZOLE STABILIZERS

The unblocked benzotriazole type aminoplast anchored stabilizers arerepresented by the formula: ##STR44## wherein A is an m functionalaminoplast anchor molecule to which n phenol rings are attached throughn methylene bridges, said bridges replacing R³, R⁴, or R⁵ groups on saidphenol rings, which aminoplast anchor molecule is selected from thegroup consisting of: ##STR45## wherein R⁷ and R⁸ are independentlyselected from the group consisting of hydrogen, alkyl of 1 to 20 carbonatoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20 carbonatoms; and wherein R⁹ is a linear or branched alkyl group of 1 to 20carbon atoms; ##STR46## wherein R¹⁰ is selected from the groupconsisting of alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbonatoms, and aralkyl of 7 to 20 carbon atoms; and wherein R⁹ is a linearor branched alkyl group of 1 to 20 carbon atoms; ##STR47## wherein R⁹ isa linear or branched alkyl group of 1 to 20 carbon atoms; ##STR48##wherein R⁹ is a linear or branched alkyl group of 1 to 20 carbon atoms;##STR49## wherein R⁹ is a linear or branched alkyl group of 1 to 20carbon atoms; ##STR50## wherein R⁹ is a linear or branched alkyl groupof 1 to 20 carbon atoms; ##STR51## wherein R⁹ is a linear or branchedalkyl group of 1 to 20 carbon atoms;

(h) oligomeric aminoplast anchor molecules derived from self- orcross-condensation of any of (a) through (g) and mixtures thereof; and

(i) mixtures of any of (a) through (h) ;

wherein m is at least 1; and wherein n is more than 0.5; and

wherein

each of R¹¹ through R¹⁴ is independently selected from the groupconsisting of alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbonatoms, aralkyl of 7 to 20 carbon atoms, hydrogen, chloro, bromo, cyano,and nitro groups;

wherein

R² is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms;

wherein

R³ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, aralkyl of 7 to 20 carbon atoms, and alkyl which isinterrupted, substituted, or interrupted and substituted by one or moreoxygen, carbonyl, or carboxy groups;

wherein

R⁴ is selected from the group consisting of hydrogen, hydroxy, alkyl of1 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 20carbon atoms, and alkyl which is interrupted, substituted, orinterrupted and substituted by one or more oxygen, carbonyl, and carboxygroups; and

wherein

R⁵ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms.

More specifically, the benzotriazole type aminoplast anchoredstabilizers may be represented by the formula: ##STR52## wherein A is anm functional aminoplast anchor molecule to which n phenol rings areattached through n methylene bridges at a point of attachment ortho- tothe point of attachment of the hydroxy group, which aminoplast anchormolecule is selected from the group consisting of: ##STR53## wherein R⁹is selected from the group consisting of methyl, ethyl, 1-propyl,2-propyl, 1-butyl, 2-butyl, and mixtures thereof; ##STR54## wherein R⁹is selected from the group consisting of methyl, ethyl, 1-propyl,2-propyl, 1-butyl, 2-butyl, and mixtures thereof; ##STR55## wherein R⁹is selected from the group consisting of methyl, ethyl, 1-propyl,2-propyl, 1-butyl, 2-butyl, and mixtures thereof;

(d) oligomeric aminoplast anchor molecules derived from self- orcross-condensation of (a), (b), (c), or mixtures thereof; and

(e) mixtures of any of (a) through (d);

wherein m is at least 1; and wherein n is more than 0.5; and

wherein

R¹² is selected from the group consisting of methyl, ethyl, methoxy,ethoxy, hydrogen, and chloro groups;

wherein

R³ is selected from the group consisting of hydrogen, methyl, ethyl,tertiary butyl, tertiary pentyl, tertiary octyl, hydroxyethyl, andbetapropionic acid esters; and

wherein

R⁴ is selected from the group consisting of hydrogen, hydroxy,hydroxyethoxy, and hydroxyhexoxy groups.

Glycoluril type aminoplasts, wherein R⁹ in the alkoxymethylglycoluril isa mixture of methyl and ethyl groups, may also be used, particularlywhen higher solubility of the product in organic solvents is desired.

The preferred benzotriazole type aminoplast anchored stabilizers arethose represented by the formula: ##STR56## wherein A is an m functionalaminoplast anchor molecule to which n phenol rings are attached throughn methylene bridges at a point of attachment ortho- to the point ofattachment of the hydroxy group, which aminoplast anchor molecule isselected from the group consisting of: ##STR57## (d) oligomericaminoplast anchor molecules derived from self- or cross-condensation of(a), (b), (c) or mixtures or thereof; and

(e) mixtures of any of (a) through (d);

wherein m is at least 1; and wherein n is more than 0.5.

Examples of the preferred embodiments are:

A. 5-Octyl substituted benzotriazoles represented by the formula:##STR58## wherein A is a glycoluril anchor; wherein m is 2 to 14 and nis in the range of from 1 to 14; wherein the ratio ofhydroxyarylbenzotriazole to glycoluril is from about 1: 1 to about 4: 1;and

wherein the glycoluril is a mixture of monomeric, dimeric, trimeric,tetrameric, and higher oligomeric units.

B. 5-Methyl substituted benzotriazoles represented by the formula:##STR59## wherein A is a glycoluril anchor; wherein m is 2 to 14 and nis in the range of from about 1 to 14; wherein the ratio ofhydroxyarylbenzotriazole to glycoluril is from about 1:1 to about 4:1;and wherein the glycoluril is a mixture of monomeric dimeric, trimeric,tetrameric, and higher oligomeric units.

AMINOPLAST ANCHORED BENZOPHENONE STABILIZERS

The unblocked benzophenone type aminoplast anchored stabilizers arerepresented by the formula: ##STR60## wherein A is an m functionalaminoplast anchor molecule to which n phenol rings are attached throughn methylene bridges, said bridges replacing R³, R⁴, or R⁵ groups on saidphenol rings, which aminoplast anchor molecule is selected from thegroup consisting of: ##STR61## wherein R⁷ and R⁸ are independentlyselected from the group consisting of hydrogen, alkyl of 1 to 20 carbonatoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20 carbonatoms, and wherein R⁹ is a linear or branched alkyl group of 1 to 20carbon atoms; ##STR62## wherein R¹⁰ is selected from the groupconsisting of alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbonatoms, and aralkyl of 7 to 20 carbon atoms; and wherein R⁹ is a linearor branched alkyl group of 1 to 20 carbon atoms; ##STR63## wherein R⁹ isa linear or branched alkyl group of 1 to 20 carbon atoms; ##STR64##wherein R⁹ is a linear or branched alkyl group of 1 to 20 carbon atoms;##STR65## wherein R⁹ is a linear or branched alkyl group of 1 to 20carbon atoms; ##STR66## wherein R⁹ is a linear or branched alkyl groupof 1 to 20 carbon atoms; ##STR67## wherein R⁹ is a linear or branchedalkyl group of 1 to 20 carbon atoms;

(h) oligomeric aminoplast anchor molecules derived from self- orcross-condensation of any of (a) through (g) and mixtures thereof; and

(i) mixtures of any of (a) through (h);

wherein m is at least 1; and wherein n is more than 0.5; and

wherein

each of R¹⁵ and R¹⁶ is independently selected from the group consistingof alkyl of 1 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms,alkoxy of 1 to 20 carbon atoms, hydrogen, chloro, bromo, cyano, nitro,and hydroxy groups;

wherein

R² is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms;

wherein

R³ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, aralkyl of 7 to 20 carbon atoms, and alkyl which isinterrupted, substituted or interrupted and substituted by one or moreoxygen, carbonyl, or carboxy groups;

wherein

R⁴ is selected from the group consisting of hydrogen, hydroxy, alkyl of1 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 20carbon atoms, and alkyl which is interrupted, substituted, orinterrupted and substituted by one or more oxygen, carbonyl, or carboxygroups; and

wherein

R⁵ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms.

More specifically, the benzophenone type aminoplast anchored stabilizersmay be represented by the formula: ##STR68## wherein A is m functionalaminoplast anchor molecule to which n phenol rings are attached throughn methylene bridges at a point of attachment ortho- or para- to thepoint of attachment of the hydroxy group, which aminoplast anchormolecule is selected from the group consisting of: ##STR69## wherein R⁹is selected from the group consisting of methyl, ethyl, 1-propyl,2-propyl, 1-butyl, 2-butyl, and mixtures thereof; ##STR70## wherein R⁹is selected from the group consisting of methyl, ethyl, 1-propyl,2-propyl, 1-butyl, 2-butyl, and mixtures thereof; ##STR71## wherein R⁹is selected from the group consisting of methyl, ethyl, 1-propyl,2-propyl, 1-butyl, 2-butyl, and mixtures thereof;

(d) oligomeric aminoplast anchor molecules derived from self- orcross-condensation of (a), (b), (c), or mixtures thereof; and

(e) mixtures of any of (a) through (d);

wherein m is at least 1; and wherein n is more than 0.5; and

wherein

each of R¹⁵ and R¹⁶ is independently selected from the group consistingof hydrogen, hydroxy, and alkoxy of 1 to 20 carbon atoms; and

wherein

R⁴ is selected from the group consisting of hydrogen, hydroxy, andalkoxy of 1 to 20 carbon atoms.

The preferred aminoplast anchor molecules are selected from the groupconsisting of: ##STR72## wherein R⁹ is selected from the groupconsisting of methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, andmixtures thereof; ##STR73## wherein R⁹ is selected from the groupconsisting of methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, andmixtures thereof;

(c) oligomeric aminoplast anchor molecules derived from self- orcross-condensation of (a), (b), or mixtures thereof; and

(d) mixtures of any of (a) through (c); and more particularly, they areselected from the group consisting of: ##STR74## (c) oligomericaminoplast anchor molecules derived from self- or cross-condensation of(a), (b) or mixtures thereof; and

(d) mixtures of any of (a) through (c);

wherein m is at least 1; and wherein n is more than 0.5.

The most preferred benzophenone type aminoplast anchored stabilizers arerepresented by the formulae: ##STR75## wherein A is a glycoluril anchor;and wherein the methylene bridge is at a point of attachment ortho- orpara- to the point of attachment of the hydroxy group; and wherein m is2 to 14 and n is in the range of from about 1 to 14, wherein the ratioof benzophenone to glycoluril is from about 1:1 to about 4:1, andwherein the glycoluril is a mixture of monomeric, dimeric, trimeric,tetrameric, and higher oligomeric units; ##STR76## wherein A is amelamine anchor; and wherein the methylene bridge is at a point ofattachment orth- or para- to the point of attachment of the hydroxygroup and wherein m is from 3 to 16 and n is in the range of 1 to 16,wherein the ratio of benzophenones to melamines is from about 1:1 toabout 6:1, and wherein the melamine is a mixture of monomeric, dimeric,trimeric, tetrameric, and higher oligomeric units.

AMINOPLAST ANCHORED ARYLTRIAZINE STABILIZERS

The unblocked aryltriazine type aminoplast anchored stabilizers arerepresented by the formula: ##STR77## wherein each of Y and Z is thesame or different aromatic carbocyclic radicals;

wherein

each of R¹⁷ through R²² is the same or different and is independentlyselected from the group consisting of alkyl of 1 to 20 carbon atoms,alkoxy of 1 to 20 carbon atoms, hydrogen, chloro, bromo, cyano, carboxy,and nitro groups; and

wherein

A is an m functional aminoplast anchor molecule to which n phenol ringsare attached through n methylene bridges, said bridges replacing R², R³,R⁴, or R⁵ groups on said phenol rings, which aminoplast anchor moleculeis selected from the group consisting of: ##STR78## wherein R⁷ and R⁸are independently selected from the group consisting of hydrogen, alkylof 1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7to 20 carbon atoms; and wherein R⁹ is a linear or branched alkyl groupof 1 to 20 carbon atoms; ##STR79## wherein R¹⁰ is selected from thegroup consisting of alkyl of 1 to 20 carbon atoms, aryl of 6 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms; and wherein R⁹ is alinear or branched alkyl group of 1 to 20 carbon atoms; ##STR80##wherein R⁹ is a linear or branched alkyl group of 1 to 20 carbon atoms;##STR81## wherein R⁹ is a linear or branched alkyl group of 1 to 20carbon atoms; ##STR82## wherein R⁹ is a linear or branched alkyl groupof 1 to 20 carbon atoms; ##STR83## wherein R⁹ is a linear or branchedalkyl group of 1 to 20 carbon atoms; ##STR84## wherein R⁹ is a linear orbranched alkyl group of 1 to 20 carbon atoms;

(h) oligomeric aminoplast anchor molecules derived from self- orcross-condensation of any of (a) through (g) and mixtures thereof; and

(i) mixtures of any of (a) through (h);

wherein m is at least 1; and wherein n is at least 0.5; and

wherein

R² is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms;

R³ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, aralkyl of 7 to 20 carbon atoms, and alkyl which isinterrupted, substituted or interrupted and substituted by one or moreoxygen, carbonyl, or carboxy groups;

R⁴ is selected from the group consisting of hydrogen, hydroxy, alkyl of1 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 20carbon atoms, and alkyl which is interrupted, substituted, orinterrupted and substituted by one or more oxygen, carbonyl, or carboxygroups; and

R⁵ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms.

More specifically, the aryltriazine type aminoplast anchored stabilizersmay be represented by the formula: ##STR85## wherein A is an mfunctional aminoplast anchor molecule to which n phenol rings areattached through n methylene bridges, said bridges replacing R³, or R⁵groups on said phenol rings, which aminoplast anchor molecule isselected from the group consisting of: ##STR86## wherein R⁹ is selectedfrom the group consisting of methyl, ethyl, 1-propyl, 2-propyl, 1-butyl,2-butyl, and mixtures thereof; ##STR87## wherein R⁹ is selected from thegroup consisting of methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl,and mixtures thereof; ##STR88## wherein R⁹ is selected from the groupconsisting of methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, andmixtures thereof;

(d) oligomeric aminoplast anchor molecules derived from self- orcross-condensation of (a), (b), (c), or mixtures thereof; and

(e) mixtures of any of (a) through (d); wherein m is at least 1; andwherein n is at least 0.5; and

wherein

each of R¹⁷ through R²² is independently elected from the groupconsisting of alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbonatoms, hydrogen, chloro, bromo, cyano, carboxy, and nitro groups;

wherein

R² is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms;

wherein

R³ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, aralkyl of 7 to 20 carbon atoms, and alkyl which isinterrupted, substituted, or interrupted and substituted by one or moreoxygen, carbonyl, or carboxy groups;

wherein

R⁴ is selected from the group consisting of hydrogen, hydroxy, alkyl of1 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 20carbon atoms, and alkyl which is interrupted, substituted, orinterrupted and substituted by one or more oxygen, carbonyl, or carboxygroups; and

wherein

R⁵ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms.

The preferred aryltriazine type aminoplast anchored stabilizers arethose represented by the formula: ##STR89## wherein A is an m functionalaminoplast anchor molecule to which n phenol rings are attached throughn methylene bridges at a point of attachment ortho- or para- to thepoint of attachment of the hydroxy groups which aminoplast anchormolecule is selected from the group consisting of: ##STR90## wherein R⁹is selected from the group consisting of methyl, ethyl, 1-propyl,2-propyl, 1-butyl, 2-butyl, and mixtures thereof; ##STR91## wherein R⁹is selected from the group consisting of methyl, ethyl, 1-propyl,2-propyl, 1-butyl, 2-butyl, and mixtures thereof; ##STR92## wherein R⁹is selected from the group consisting of methyl, ethyl, 1-propyl,2-propyl, 1-butyl, 2-butyl, and mixtures thereof;

(d) oligomeric aminoplast anchor molecules derived from self- or cross-condensation of (a), (b), (c), or mixtures thereof; and

(e) mixtures of any of (a) through (d);

wherein m is at least 1; and wherein n is more than 0.5; and

wherein

R²⁵ is selected from the group consisting of hydrogen, linear, branchedor cyclic alkyl of 1 to 20 carbon atoms, and alkyl which is interrupted,substituted, or interrupted and substituted by one or more oxygen,carbonyl, and carboxy groups.

The preferred aminoplast anchor molecules are selected from the groupconsisting of: ##STR93## (d) oligomeric aminoplast anchor moleculesderived from self- or cross-condensation of (a), (b), (c), or mixturesthereof; and

(e) mixtures of any of (a) through (d).

An example of the preferred embodiment of the aryltriazine typestabilizers is represented by the formula: ##STR94## wherein A is aglycoluril anchor; and wherein R²⁶ is a linear, branched, or cyclicalkyl of 6 to 12 carbon atoms or mixtures thereof; wherein the methylenebridge is at a point of attachment ortho- or para- to the point ofattachment of the hydroxy group; and wherein m is 2 to 14, and n is inthe range of 1 to 14, wherein the ratio of hydroxyaryltriazines toglycolurils is from about 1:1 to about 4:1, and wherein the glycolurilis a mixture of monomeric, dimeric, trimeric, tetrameric, and higheroligomeric units.

AMINOPLAST ANCHORED BLOCKED OXANILIDE STABILIZERS

The blocked oxanilide UV stabilizers of the invention are represented bythe formula: ##STR95## wherein A is an m functional aminoplast anchormolecule to which n phenol rings are attached through n methylenebridges, said bridges replacing R³, R⁴, or R⁵ groups on said phenolrings, which aminoplast anchor molecule is selected from the groupconsisting of: ##STR96## wherein R⁷ and R⁸ are independently selectedfrom the group consisting of hydrogen, alkyl of 1 to 20 carbon atoms,aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms; andwherein R⁹ is a linear or branched alkyl group of 1 to 20 carbon atoms;##STR97## wherein R¹⁰ is selected from the group consisting of alkyl of1 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7 to20 carbon atoms; and wherein R⁹ is a linear or branched alkyl group of 1to 20 carbon atoms; ##STR98## wherein R⁹ is a linear or branched alkylgroup of 1 to 20 carbon atoms; ##STR99## wherein R⁹ is a linear orbranched alkyl group of 1 to 20 carbon atoms; ##STR100## wherein R⁹ is alinear or branched alkyl group of 1 to 20 carbon atoms; ##STR101##wherein R⁹ is a linear or branched alkyl group of 1 to 20 carbon atoms;##STR102## wherein R⁹ is a linear or branched alkyl group of 1 to 20carbon atoms;

(h) oligomeric aminoplast anchor molecules derived from self- orcross-condensation of any of (a) through (g) and mixtures thereof; and

(i) mixtures of any of (a) through (h);

wherein m is at least 1; and wherein n is more than 0.5; and

wherein

each of R²³ and R²⁴ is the same or different and is independentlyselected from the group consisting of alkyl of 1 to 20 carbon atoms,aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms,hydrogen, chloro, bromo, cyano, and nitro groups;

wherein

R² is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms;

R³ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, aralkyl of 7 to 20 carbon atoms, and alkyl of 1 to 20carbon atoms which is interrupted, substituted, or interrupted andsubstituted by one or more oxygen, carbonyl, or carboxy groups;

R⁴ is selected from the group consisting of hydrogen, hydroxy, alkyl of1 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 20carbon atoms, and alkyl of 1 to 20 carbon atoms which is interrupted,substituted, or interrupted and substituted by one or more oxygen,carbonyl, or carboxy groups;

R⁵ is selected from the group consisting of hydrogen, alkyl of 1 to 20carbon atoms, and aralkyl of 7 to 20 carbon atoms; and

R⁶ is a blocking group selected from the group consisting of alkyl of 1to 20 carbon atoms, acyl of 1 to 20 carbon atoms, alkylaminocarbonyl of1 to 20 carbon atoms, arylaminocarbonyl of 6 to 20 carbon atoms, andtrisubstituted silyl groups.

More specifically, the blocked oxanilide type aminoplast anchoredstabilizers of the invention are represented by the formula: ##STR103##wherein A is an m functional aminoplast anchor molecule to which nphenolic rings are attached through n methylene bridges, said bridgesreplacing hydrogen groups on said phenolic rings, which aminoplastanchor molecule is selected from the group consisting of: ##STR104##wherein R⁹ is selected from the group consisting of methyl, ethyl,1-propyl, 2-propyl, 1-butyl, 2-butyl, and mixtures thereof; ##STR105##wherein R⁹ is selected from the group consisting of methyl, ethyl,1-propyl, 2-propyl, 1-butyl, 2-butyl, and mixtures thereof; ##STR106##wherein R⁹ is selected from the group consisting of methyl, ethyl,1-propyl, 2-propyl, 1-butyl, 2-butyl, and mixtures thereof;

(d) oligomeric aminoplast anchor molecules derived from self- orcross-condensation of (a), (b), (c), or mixtures thereof; and

(e) mixtures of any of (a) through (d);

wherein m is at least 1; and wherein n is more than 0.5; and

wherein

R²³ is selected from the group consisting of alkyl of 1 to 20 carbonatoms, aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms,hydrogen, chloro, bromo, cyano, and nitro groups; and

R⁶ is a blocking group selected from the group consisting of alkyl of 1to 20 carbon atoms, acyl of 1 to 20 carbon atoms, alkylaminocarbonyl of1 to 20 carbon atoms, arylaminocarbonyl of 6 to 20 carbon atoms, andtrisubstituted silyl groups.

The preferred blocked oxanilide stabilizers of the invention are thosewherein R⁶ is selected from the group consisting of ethyl, acetyl,phenylaminocarbonyl, dodecylaminocarbonyl, and trimethylsilyl groups.

An example of the blocked oxanilide type stabilizers of the invention isrepresented by the formula: ##STR107## wherein A is a glycoluril anchor;and wherein m is 2 to 14 and n is in the range of from about 1 to about14, wherein the methylene bridge is ortho- para-, or a mixture of ortho-and para- to the oxygen of the phenolic ring, wherein the ratio ofoxanilide to glycoluril is from about 1:1 to about 4:1, and wherein theglycoluril is a mixture of monomeric, dimeric, trimeric, tetrameric, andhigher oligomeric units.

PROCESS FOR PREPARATION

The aminoplast anchored monomeric or oligomeric stabilizers of theinvention are prepared by contacting a monomeric or oligomericaminoplast anchor A usable in this invention as described hereinabove inthe section entitled "Aminoplast Anchors" with at least one blocked orunblocked phenolic stabilizer usable in the invention as describedhereinabove in the section entitled "Phenolic Stabilizers" in aconcentrated sulfuric acid reaction medium.

The novel process of the invention may employ any stabilizer toaminoplast ratio and is not restricted to the greater than 0.5:1phenolic stabilizer to aminoplast ratio of the novel compositions ofmatter described previously in the section entitled "Anchored Products".Stabilizers having greater than 0.5:1 phenolic stabilizer to aminoplastratios may certainly be prepared by the process of the invention, butstabilizers having less than 0.5:1 phenolic stabilizer to aminoplastratios, such as a ratio of 0.01:1, may also be prepared by the processof the invention. The preferred stabilizer to aminoplast ratio isgreater than 1:1, and the most preferred ratio is greater than 2:1.

The driving force for the acid catalyzed reaction between the reactantsis the generation, from the alkoxymethylated or hydroxymethylatedaminoplast reactant, of a positively charged electrophilic center on themethylene group of the alkoxymethyl or hydroxymethyl attached to theaminoplast by elimination of the elements of an alcohol or water from aprotonated aminoplast. The positively charged electrophilic center thenproduces an anchored stabilizer of the invention by an electrophilicaromatic substitution reaction at the most electron rich, unblockedcenter of the phenolic stabilizer, usually ortho- or para- to thephenolic oxygen, or a mixture thereof. When a reactive ortho- site isblocked with a substituent group, then the para-position is attacked bythe electrophile. When both ortho- and para-positions are blocked bysubstituent groups, then an unblocked position meta- to the phenolicoxygen may be substituted. In general, the aromatic hydrogens are themost easily substituted moieties on the phenol ring. However, otherlabile groups such as tertiary butyl and tertiary octyl groups may alsobe electrophilically substituted. When, in addition to the phenolicoxygen, a multiplicity of substituents are present on the phenolic ring,some being electron releasing and others being electron withdrawing,then the sum of all effects will determine the electrophilic aromaticsubstitution reaction site on the phenolic ring in accordance with thewell established principles of orientation in electrophilic aromaticsubstitution chemistry. Some of the basic principles of electrophilicaromatic substitution chemistry are described by R. O. C. Norman in"Principles of Organic Synthesis", 2nd Edition, Chapman and Hall, London(1978), in the chapter entitled "Electrophilic Aromatic Substitution"under the heading "Directire and Rate Controlling Factors", pages 370 to377.

Alkoxymethylated aminoplasts are known to undergo self condensationreactions when exposed to acids, and particularly when exposed to acidsand heat. The product of the self condensation reaction is an oligomericalkoxymethylated aminoplast if the starting aminoplast is monomeric.Similarly, if the starting aminoplast is oligomeric, then higheroligomers are produced by the self condensation reaction.

It is the surprising discovery of this invention that when the acid usedin the process of the invention is concentrated sulfuric acid, andparticularly when concentrated sulfuric acid is used as the reactionmedium in which the aminoplast anchor is contacted with the phenolicstabilizer, the expected self-condensation reaction of the aminoplastsis suppressed such that only relatively low levels of oligomericproducts result.

As a consequence of suppressed self-condensation, the aminoplastanchored stabilizers prepared by the process of this invention comprise,in addition to the monomers, only lower oligomeric components such asdimers, trimers, and occasionally tetramers. While it is possible, invery rare cases, to obtain higher oligomers, oligomers higher thantetramers generally are not obtained. By varying the reactionconditions, however, it is possible to control the degree ofoligomerization to produce higher or lower oligomeric anchoredstabilizers.

Because the self condensation reaction of alkoxymethylated aminoplastsproceeds concurrently and competitively with the electrophilic aromaticsubstitution reaction on the phenolic stabilizers, products with varyingdegrees of oligomerization may be obtained depending on the reactioncondition, particularly the mode of addition of reactants used in theprocess of the invention. Thus, adding the phenolic stabilizer reactantto a mixture of the alkoxymethylated aminoplast and acid will produce aproduct more highly oligomeric than employing a mode of addition whereinan alkoxymethylated aminoplast is gradually added to a mixture of thephenolic stabilizer reactant and the acid. The mode of addition whereinthe aminoplast is added to the remaining ingredients produces the leastamount of oligomeric products. The product therefore has an overall lowdegree of oligomerization.

A mode of addition wherein the acid is added to a mixture of theaminoplast and the phenolic stabilizer reactants will have anintermediate degree of oligomerization.

The reaction is conducted by contacting the named reactants in anyconvenient manner in liquid concentrated sulfuric acid reaction mediumhaving a sulfuric acid concentration of at least 75 weight percent.

The reaction may be conducted as a batch or as a continuous process atthe convenience of the operator. The number of moles of the phenolicstabilizer per each aminoplast alkoxymethyl group in the product istypically in the range of from 0.01:1 to 1.2:1. The anchored product maybe isolated by precipitation from cold water or it may be extracted withan organic solvent by known techniques.

The process of the invention comprises contacting an alkoxymethylatedaminoplast with a phenolic stabilizer in the presence of sulfuric acidas the reaction medium at a temperature and for a length of timesufficient to produce the novel monomeric or oligomeric aminoplastanchored stabilizers of the invention.

The process is carried out typically at a temperature in the range of-15° C. to 50° C., although temperatures which are lower or higher mayalso be used. The preferred temperature, however, is from about 0° C. toabout 26° C.

The process is carried out for a period of time typically in the rangeof from about 5 minutes to about 5 hours, although shorter or longerperiods may also be used. The preferred time, however, is from about 30minutes to about 3 hours.

CURABLE COMPOSITION

The novel compositions of matter described above are useful asultraviolet (UV) stabilizer additives to polymers, particularly asadditives to thermoplastic polymers and thermoset systems. They may beadded to the polymer to impart useful stabilizing properties to thepolymer by themselves or in combination with antioxidant or hinderedamine stabilizers.

In thermoplastic polymer applications stabilizing polymers such aspolyethylene, polypropylene, polyvinylchloride, polystyrene,polycarbonates, polyurethanes, polyamides, and the like, the novelaminoplast anchored stabilizers of the invention are simply incorporatedinto thermoplastic materials at a level in the range of about 0.01 toabout 5 weight percent by methods known in the art.

In thermoset coating applications, the aminoplast anchored stabilizersof the invention are used to prepare a novel curable composition whichcomposition is thereafter cured to produce light stable films andobjects.

The novel curable composition of the invention comprises:

(i) a stabilizingly effective amount of a stabilizer comprising anaminoplast anchor having more than 0.5 mole of phenolic stabilizer groupper mole of aminoplast pendently attached thereto;

(ii) a crosslinkingly effective amount of a crosslinking agent; and

(iii) a polyfunctional, active hydrogen containing material.

The preferred curable compositions comprise a stabilizer (i), which is astabilizer of the invention, in an amount of at least 0.01 weightpercent of the total weight of the curable composition.

Typically, the novel curable composition of the invention comprises:

(i) about 0.01 to 5 weight percent of a novel stabilizer of theinvention;

(ii) about 3 to 55 weight percent of a crosslinking agent; and

(iii) about 40 to 97 weight percent of a polyfunctional active hydrogencontaining material.

The curable composition, optionally, may contain a cure catalyst toaccelerate curing.

The novel stabilizers of the invention are described hereinabove in thesection entitled "Anchored Products". They may be blocked or unblocked,monomeric or oligomeric, or they may be mixtures.

The crosslinking agent may be an aminoplast crosslinking agent selectedfrom unetherified, partially etherified or fully etherified aminoplastresins, or it may be any mixture thereof.

The aminoplast crosslinkers are described above in the section entitled"Aminoplast Anchors" and include crosslinkers such as CYMEL® 1130 resin,CYMEL® 303 resin, CYMEL® 1170 resin, POWDERLINK® 1174 resin, CYMEL® 1123resin, and the like.

The polyfunctional active hydrogen containing material comprises atleast one class of active hydrogen functionality selected from the groupconsisting of carboxy, hydroxy, amido, mercapto, and a group convertiblethereto. The hydroxy and carboxy functional groups are preferred.

Especially suitable polyfunctional active hydrogen containing materialsinclude polyesters, polyacrylates, polyurethane polyols, and products ofcondensation of amines with epoxy resins, all containing hydroxy groupsas reaction sites. The polyesters are obtained in a known manner by, forexample, the reaction of polyfunctional carboxylic acids with excessquantities of polyhydric alcohols; the polyacrylates are obtained by thecopolymerization of acrylic or methacrylic acid derivatives with hydroxygroup containing derivatives of these acids, such as, for example, thehydroxyalkyl esters, optionally with the simultaneous use of additionalvinyl compounds, such as, for example, styrene. The hydroxy groupcontaining polyurethanes can be obtained, in a known manner, by thereaction of polyisocyanates with excess quantities of compoundscontaining at least two hydroxy groups.

Suitable commercially available hydroxy group containing polyesters areCYPLEX® 1531, a polyester of phthalic acid, adipic acid, ethanediol, andtrimethylol propane from American Cyanamid Company, Cargil Polyester5776, available from Cargil, and TONE® 0200 available from Union CarbideCorp. Suitable hydroxy functional acrylic resins are availablecommercially from S. C. Johnson & Son, Inc. under the trademark JONCRYL®500, a copolymer of styrene, hydroxypropyl methacrylate and butylacrylate, and from Rohm & Hass Co. under the trademark AT-400. Alsosuitable for use are hydroxy-terminated polycaprolactones.

The hydroxyfunctional polyfunctional active hydrogen containing materialcomprises compounds and resins selected from acrylic resins, polyesterresins, polyurethanes, polyols, products derived from the condensationof epoxy resins with amines, and mixtures thereof.

A cure catalyst to accelerate the crosslinking reaction may be alsooptionally used, however, the curable compositions of the invention arecapable of curing without an added catalyst.

When a catalyst is present, crosslinking takes place more rapidly at aparticular temperature than when a catalyst is not present. Typically,crosslinking is effected at a lower temperature with a catalyst present.

The acid cure catalysts usable in the invention include carboxylic acidssuch as phthalic and oxalic acids; sulfonic acids such aspara-toluenesulfonic acid, dinonyl naphthalenesulfonic acid, naphthalenesulfonic acid, dodecylbenzenesulfonic acid; phosphonic acids; mineralacids such as nitric acid, sulfuric acid, phosphoric acid,polyphosphoric acid, and the like. The use of a sulfonic acid ispreferred.

When employed, the cure catalyst is used in the curable compositions ofthe invention in amounts effective to accelerate cure at the temperatureemployed. For example, the catalyst is typically used in amounts of fromabout 0.01 to about 2.0% by weight, with 0.02 of 1% by weight, based onthe weight of the curable compositions, being preferred.

In the practice of the invention, the curable compositions can beadapted for use in solvent-based, water-based, and powder coatingapplications. They may also be used in molding applications. Sulfonimidecatalysts are particularly well suited for use in powder coatingapplications.

The curable compositions of the invention may also contain otherstabilizers such as monomeric or oligomeric hindered amine lightstabilizers (HALS), phenolic antioxidants, phosphite antioxidants,sulfur containing antioxidants such as sulfides and disulfides, other UVabsorbers, acid scavengers, fillers, pigments, flame retardants, and thelike.

METHOD OF USING

This invention is also an improved method of using the aminoplastanchored novel stabilizers of the invention described above in thesection entitled "Anchored Products." The method utilizes the novelcurable compositions of the invention also described above in thesection entitled "Curable Compositions."

The novel method described herein is an improved method of coatingsubstrates of the type having the steps of (I) contacting said substratewith a conventional curable composition containing a stabilizer, acrosslinking agent, and a polyfunctional active hydrogen containingmaterial, and (II) thereafter curing said conventional curablecomposition, wherein the improvement comprises:

(a) contacting said substrate with a novel curable compositioncomprising:

(i) a stabilizingly effective amount of a stabilizer comprising anaminoplast anchor having more than 0.5 mole of phenolic stabilizer groupper mole of aminoplast pendently attached thereto;

(ii) a crosslinkingly effective amount of a crosslinking agent; and

(iii) a polyfunctional active hydrogen containing material; and

(b) thereafter curing said novel curable composition. The substrate tobe coated may be selected from surfaces such as steel, aluminum, plasticmaterials, and the like. Alternatively, a mold may be used instead of asurface to practice the method of the invention.

The contacting of a substrate with the novel curable composition of theinvention may be carried out by any of the conventional coating methodsincluding spraying, padding, brushing, electrostatic spraying as is thecase in powder coatings, roller coating, curtain coating, flow coating,dipping, and electrocoating.

The curing may be carried out by continued application of heat at anelevated temperature or at an ambient temperature.

The cure may be accelerated by the use of a suitable catalyst such asthose used to cure the novel curable compositions.

STABILIZED ARTICLES

The novel method of using the anchored stabilizers of the inventionaccording to the method described above produce a product, which, inthis case, is a crosslinked article in the form of a film such ascoatings, or it is in the form of an article such as a molded product.

The cured compositions may be used as coatings for wire, appliances,automotive parts, furniture, pipes, machinery, and the like. Surfaceswhich are suitable include plastics, wood, and metals such as steel,aluminum, and the like.

The cured compositions may also be used to form solid articles such ascases, enclosures, and structural members.

The following examples illustrate the preparation and use of the novelstabilizers of the invention by the process of the invention. Theseexamples are not, however, intended to limit the claims in any mannerwhatsoever.

EXAMPLE 1

Recrystallized solid POWDERLINK® 1174 resin* having the chemical nametetramethoxymethyl glycoluril (8.0 g, 0.025 mole) was added, over aperiod of 20 minutes, to a mixture of cooled (10° C.) and vigorouslystirred solution of CYASORB® UV 5411 ultraviolet light stabilizer**having the chemical name of2-(2-hydroxy-5-tertiary-octylphenyl)benzotriazole (32.2 g, 0.1 mole) and98% sulfuric acid (90 ml) under a nitrogen blanket, while maintainingthe temperature of the reaction mixture at 12° to 16° range. After theaddition was complete, the temperature of the reaction mixture wasallowed to rise to 23° C. over a period of 45 minutes and when then keptat ambient temperature for an additional 80 minutes. The resultingreddish to orange colored solution was poured onto cold (0° C.) water(500 ml) with vigorous, high shear agitation. The light yellow colored,finely dispersed solid precipitate was collected by filtration andwashed with cold water or dilute aqueous sodium bicarbonate and thenwith cold methanol containing 10 weight percent water. The washing stepswere repeated until a 15 weight percent solution of the product inxylenes had a clear appearance indicating that the product wasessentially free of salt impurities.

After drying at 70° C. under reduced pressure, a light tan colored,fine, powdery material was obtained in near quantitative yield (39.8 g).The following characteristics were determined experimentally:

(1) The product was readily soluble in organic solvents such as toluene,xylene, tetrahydrofuran, and dimethylsulfoxide.

(2) The product was soluble in amino resins such as CYMEL® 1133 resin*,at a level of at least 20 weight percent. Preparation of even a 10weight percent solution of2-(2-hydroxy-5-tertiaryoctylphenyl)benzotriazole, in contrast, waspossible only when the mixture of the triazole and CYMEL® 1133 resin washeated. Upon cooling to room temperature, however,2-(2-hydroxy-5-tertiaryoctylphenyl)benzotriazole crystallized out of thesolution, indicating incompatibility with CYMEL® 1133 resin which is atypical melamine-formaldehyde resin used extensively in coatings. It isconcluded from the above comparison of solubility behavior of theaminoplast anchored benzotriazole with its unanchored precursor that thecompatibility of a benzotriazole is substantially increased by anchoringsaid benzotriazole onto an aminoplast anchor molecule.

(3) The product was free of tetramethoxymethylglycoluril startingmaterial as indicated by High Performance Size Exclusion Chromatography(HPSEC) tracing experiments.

(4) The product contained 1.6 percent by weight unreacted2-(2-hydroxy-5-tertiaryoctylphenyl)benzotriazole starting material asindicated by HPSEC tracing experiments.

(5) The product comprised monomeric, dimeric, trimeric, and tetramericcomponents as indicated by an excellent agreement between the measuredmolecular weight as determined by Vapor Phase Osmometry (VPO) and themolecular weight calculated by taking into account the relativecontributions of each component present in the product according totheir relative peak areas in the HPSEC output.

(6) The product had a benzotriazole to methoxymethyl molar ratio of 50:1as determined by Nuclear Magnetic Resonance Spectroscopy (NMR)indicating greater than 98% conversion of the methoxymethyl groups tomethylene bridge groups.

(7) The product exhibited a strong infrared absorption band at 875 cm⁻¹,an absorption far greater in intensity than the starting benzotriazoleabsorption in the same region. The 875 cm⁻¹ absorption in the aminoplastanchored product is assigned to the two hydrogens meta- to the hydroxygroup, whereas in the starting benzotriazole, the strong band at 820cm⁻¹ is assigned to two adjacent hydrogens on the phenol ring (viz.ortho- and meta- to the hydroxy group). It is concluded from the aboveobservations in the infrared spectrum of the starting material and thereaction product, that reaction had indeed occurred between themethoxymethyl group of the glycoluril and the phenol ring of thebenzotriazole, forming a new C--C bond at the position ortho- to thephenolic hydroxy. The above conclusion is further supported by thecomplete disappearance of the 820 cm⁻¹ absorption band, present in thestarting benzotriazole, from the infrared spectrum of the product whichno longer has adjacent hydrogens.

(8) The product also exhibited, in its ultraviolet spectrum, abathochromic shift, 6 nano-meters in magnitude, to longer wavelengthsrelative to the starting benzotriazole: 303 nm in the product, versusthe 297 nm in the starting material, as expected on the basis of anortho-methylene bridging. Based on the above facts and observations, weconclude that the data presented above provide clear and convincingproof in support of the structure suggested for the novel aminoplastanchored stabilizers of the invention.

EXAMPLE 2

The procedure of Example 1 was repeated using 9.5 g of CYMEL® 1171resin*, a product of American Cyanamid Company, Wayne, N.J., instead ofthe tetramethoxymethylglycoluril resin (POWDERLINK® 1174) used inExample 1, with the exception that the salt impurities were removed byreslurrying the product in water (600 ml) at ambient temperatures, withvigorous agitation for about 1 hour, filtering, and repeating thereslurrying step at 80° to 85° C. and filtering to give, after drying, aglycoluril anchored benzotriazole stabilizer in near quantitative yield(36.1 g). The product was very similar to the product obtained in theprocedure of Example 1. It had the following additional characteristics:

(1) The product contained 0.7 weight percent unreacted2-(2-hydroxy-5-tertiaryoctylphenyl)benzotriazole starting material asdetermined by HPSEC.

(2) The product contained 1.2 weight percent unreacted CYMEL® 1171 resinas determined by HPSEC.

(3) The product exhibited a thermogravimetric volatility profile (TGA)indicative of 5% weight loss on heating to 300° C.

(4) The product had a total acidity of 0.15 milliequivalent per gram ofproduct as determined by potentiometric titration.

This example illustrates the preparation of another glycoluril anchoredbenzotriazole stabilizer of the invention using mixedalkoxyalkylglycoluril as the starting aminoplast anchor molecule.

EXAMPLE 3

The procedure of Example 1 was repeated using 12.5 g of CYMEL® 300resin,* a product of American Cyanamid Company, Wayne, N.J., instead ofthe POWDERLINK® 1174 resin, with the exception that the filtered productwas:

(1) washed with dilute aqueous sodium bicarbonate solution,

(2) slurried in an 8:2 ratio of a methanol-water mixture (400 ml),

(3) agitated at room temperature for about 3.5 hours,

(4) after filtering and drying as described in Example 1, it wasredissolved in xylenes and the insoluble salts were removed byfiltration, and

(5) the xylenes were removed by distillation under reduced pressure.

The residue was a melamine anchored benzotriazole stabilizer, an exampleof the novel stabilizers of the invention.

The product contained about 2 weight percent of unreacted CYASORB® UV5411 stabilizer as determined by HPSEC.

EXAMPLE 4

The procedure of Example 1 was repeated using 19.6 g of CYMEL® 1123resin*, a product of American Cyanamid Company, Wayne, N.J., instead ofthe POWDERLINK® 1174 resin, with the exception that the filtered productwas washed several times with dilute aqueous sodium bicarbonatesolution. Analysis of the product at this stage by HPSEC indicated thatno benzotriazole starting material was present. There was present,however, about 3.5 weight percent unreacted CYMEL® 1123 resin.

The crude product was further purified by reslurrying the product in87.5 weight percent aqueous methanol (400 ml) with agitation at roomtemperature for 5 hours. Filtering, washing with methanol, and dryinggave a light tan colored powder (41.4 g) having a total acidity of 0.23milliequivalent per gram of product as determined by potentiometrictitration.

EXAMPLE 5

The procedure of Example 1 was repeated using half the amount ofPOWDERLINK® 1174 resin (4.0 g, 0.0125 mole) with the exception thatCYASORB®UV 1164 stabilizer* (2.5.5g, 0.050 mole) was used instead ofCYASORB® UV 5411.

The crude reaction product contained 1.1 weight percent unreactedCYASORB® UV 1164 stabilizer as determined by HPSEC. To further purifythe product, the crude product was reslurried in 90 weight percentaqueous methanol (400 ml) with agitation for 1.5 hours at roomtemperature, filtered, and dried to give a light yellow powder (29.8 g)having a total acidity of 0.23 milliequivalent per gram as determined bypotentiometric titration.

The product was soluble in CYMEL® 1133 resin at room temperature at a 10weight percent level producing clear solutions. In contrast, thestarting CYASORB® UV 1164 stabilizer gave turbid solutions even at thelower, 5 weight percent levels. This demonstrates the increasedcompatibility of the aminoplast anchored CYANSORB® UV 1164 stabilizer ofthe invention over its precursor in a coating system such as CYMEL®1133, which is a typical melamine resin widely used in coatings.

EXAMPLE 6

The procedure of Example 1 was repeated using:

(1) CYASORB® 1164 stabilizer (51.0 g, 0.10 mole) instead of CYASORB® UV5411, and

(2) using CYMEL® 1171 resin (9.5 g) instead of the POWDERLINK® 1174resin.

The crude reaction product was reslurried in water, and then diluteaqueous sodium bicarbonate was added, then stirred, the solids filtered,and washed. The purification cycle was repeated to give a dried product(54.3 g) having a total acidity of 0.17 milliequivalent per gram asdetermined by potentiometric titration. The product contained 1.1 weightpercent unreacted starting CYASORB® UV 1164 stabilizer as determined byHPSEC.

EXAMPLE 7

The procedure of Example 1 was repeated using CYASORB® UV 531stabilizer* (32.6 g, 0.10 mole) instead of CYASORB® UV 5411 stabilizer.The washed product melted during the drying step but resolidified uponcooling to give a yellow, brittle mass which was readily soluble inorganic solvents such as acetone, tetrahydrofuran, xylenes, and toluene,but only partially soluble in methanol or higher alcohols. The producthad total acidity of 0.19 milliequivalent per gram of product asdetermined by potentiometric titration. The product also contained asmall amount (less than 0.5 weight percent) of unreacted CYASORB® UV 531stabilizer as determined by HPSEC.

The product was further purified by dissolving in xylenes and addinghexane to precipitate the glycoluril anchored4-n-octoxy-2-hydroxybenzophenone stabilizer of the invention.

EXAMPLE 8

The procedure of Example 1 was repeated using CYASORB® UV 531 stabilizer(32.69, 0.10 mole) instead of CYASORB® UV 5411, and using CYMEL® 300resin (8.2 g) instead of the POWDERLINK® 1174 resin. After washing,bicarbonate treatment, and reslurrying several times, the yellow productsolidified on cooling to a brittle mass. The product contained nostarting CYASORB® UV 531 stabilizer, but a small amount (less than 1weight percent) of unreacted CYMEL® 300 resin was detected by HPSEC.

EXAMPLE 9

To cooled (ice bath) concentrated sulfuric acid (80 ml) in a 250 mlthree neck flask equipped with a thermometer, agitator and nitrogeninlet, 45.29 (0.1 m) of SANDOVUR® 3206 oxanilide absorber, a product ofSandoz Corp., was added over a period of 10 minutes at 6° to 12° C.temperature range with stirring. CYMEL® 1171 resin 9.8 g (0.031 m) wasthen added over a period of 10 minutes while maintaining a temperaturein the 8° to 16° C. range. The reaction mixture was kept at 15°-17° C.for 50 minutes, and then the temperature was allowed to rise to 25° C.,and the mixture was allowed to stand for another 50 minutes. The productwas precipitated by pouring the reaction mixture over 500 g of ice waterunder vigorous agitation. After cold and hot water extractions, theproduct was collected and dried under reduced pressure at 85° C. HighPerformance Size Exclusion Chromotography (HPSEC) revealed the presenceof four major fractions, attributed to monomeric (16%), dimeric (8%),trimeric (54%), tetrameric (17%), and higher oligomeric (5%) components.The Fourier-Transform Infrared Spectrum (FTIR) indicated that theelectrophilic substitution had taken place in the ortho- andpara-positions relative to the point of attachment of the ethoxy groupsin about 40:60 ratio.

EXAMPLE 10

POWDERLINK® 1174 resin (0.8 g, 0.0025 mole) was added to a mixture ofsalicylic acid (1.38 g, 0.010 mole) and concentrated sulfuric acid (14ml) at about 15° C. The mixture was then allowed to warm to roomtemperature overnight and then poured over ice water (100 g) to give awhite precipitate which was collected by filtration to give a product(76% yield) which contained the methylene bridged adducts.

EXAMPLE 11

The procedure of Example 1 is repeated with the exception that insteadof the 0.1 mole of CYASORB® UV 5411 stabilizer reactant used in Example1, a mixture of CYASORB® UV 5411 (16.1 g, 0.05 mole) and CYASORB® UV 531(16.3 g, 0.05 mole) is used as the stabilizer reactant. POWDERLINK® 1174(8.0 g, 0.025 mole) is used as the aminoplast reactant. The productobtained contains a POWDERLINK® 1174 anchored stabilizer wherein thependant stabilizer group is a mixture of CYASORB® UV 5411 and CYASORB®UV 531 stabilizers present in approximately equimolar quantities.

EXAMPLE 12

A set of six white pigmented acrylic based coat-clear coat panels wereprepared using CYMEL® 1130 resin as the crosslinking agent using thefollowing conditions:

    ______________________________________                                        PIGMENTED BASE COAT                                                           Acryloid ® AT-400/CYMEL ® 1130 Ratio                                                           60/40                                                OR-650 Pigment/Binder Ratio                                                                            0.8                                                  para-Toluenesulfonic Acid, Weight % on                                                                 0.4                                                  TRS (total resin solids)                                                      normal Butanol, Weight % on TRS                                                                        20                                                   Non-Volatiles, weight % (Xylene makeup)                                                                65                                                   Substrate                BO 100 CRS                                           Schedule                 20 min/100° C.                                CLEAR COAT                                                                    ACRYLOID ® AT-400/CYMEL ® 1130 Ratio                                                           60/40                                                para-Toluensulfonic Acid, Weight % on                                                                  0.3                                                  TRS                                                                           normal Butanol, Weight % on TRS                                                                        20                                                   Xylene Make-up Containing Test                                                                         65                                                   Stabilizers Non-volatiles, Weight %                                           Film Thickness (#46 Applicator), mils                                                                  1.75                                                 mm                       0.044                                                Schedules, Standard      30 min/121° C.                                Overbake                 Standard Plus                                                                 30 min/177° C.                                ______________________________________                                    

The test stabilizers were added as 18 weight % solutions in xylene tothe fully formulated clear coat composition at a 6 weight percentloading of "active" CYASORB® UV 5411 based on CYMEL® 1130 resin solely.The test stabilizers used and the base coat/clear coat cured coatingsderived therefrom by curing under normal and overbake conditions arelisted below:

    ______________________________________                                        AMINOPLAST          COATINGS                                                  ANCHORED STABILIZERS                                                                              NORMAL    OVERBAKE                                        AMINOPLAST          COATINGS                                                  ANCHORED STABILIZERS                                                                              NORMAL    OVERBAKE                                        ______________________________________                                        (1) CYASORB ® UV 5411/                                                                            A         G                                               POWDERLINK ® 1171 (3:1                                                    Ratio)*                                                                   (2) CYASORB ® UV 5411/                                                                            B         H                                               POWDERLINK ® 1174                                                         (4:1 Ratio)*                                                              (3) CYASORB ® UV 5411/                                                                            C         I                                               CYMEL ® 300 (3:1 Ratio)*                                              (4) CYASORB ® UV 5411/                                                                            D         J                                               CYMEL ® 1123 (3.8:1 Ratio)*                                           (5) CYASORB ® UV 5411                                                                             E         K                                               (Control) Stabilizer                                                      (6) No Stabilizer Additives (Blank)                                                                   F         L                                           ______________________________________                                         *Molar Ratios.                                                           

Coatings A through J were exposed to ultraviolet light in a QUV unit,available from Q-Panel Company, Cleveland, Ohio, for the purpose ofcarrying out an accelerated exposure test. The QUV data was generated at8 hours UV exposure at 70° C., followed by 4 hours condensation at 50°C. cycle, hereinafter "GM Cycle."The test was terminated after 2500hours total time.

Examination of the QUV exposed coatings with respect to gloss, yellowindex, distinctness of image (DOI), and cracking (see Table 1) revealedthat coatings G and H did not exhibit any cracking under GM cycle.Coatings G and H outperformed all others in the overbake series, withcoating H outperforming coating G. Under overbake conditions, coating Kwas the worst, except for coating L (blank) which was not stabilized. Inthe case of coating K, CYASORB® UV 5411, being volatile, was depletedduring overbake.

In the normal series, coating E outperformed only coating D by a slightmargin. Coatings A, B, and C all outperformed coating E, with coating Boutperforming all others in gloss, yellow index, distinctness of image(DOI), and cracking.

It is concluded from the QUV exposure data (Table 1) that:

(1) aminoplast anchored stabilizers are superior to their unanchoredprecursors, particularly under overbake conditions, due to their reducedvolatility as a result of increased molecular weight;

(2) POWDERLINK® 1174 anchored stabilizers are superior to all others;

(3) anchored stabilizers having high stabilizer/aminoplast ratios aresuperior to those having lower ratios even when used at identical"active" stabilizer levels; and

(4) anchored stabilizers have superior permanence in the film than theirunanchored precursors under normal and overbake conditions. This ismanifested by a 100% ultraviolet absorption retention of coatings B andH versus only 30% absorption retention of coating E (normal bakeconditions) and 0% absorption retention of coating K (overbakeconditions).

                                      TABLE 1                                     __________________________________________________________________________    QUV EXPOSURE BEHAVIOR OF AMINOPLAST                                           ANCHORED CYASORB ® UV 5411 STABILIZED                                     BASE COAT/CLEAR COAT COATINGS                                                           20° Gloss %                                                                     Distinctiveness of Image %                                                                  Yellow Index                                           Initial                                                                           Final                                                                              Initial                                                                              Final  Initial                                                                           Final     Cracking Rating                COATINGS  O HR                                                                              2457 HR                                                                            O HR   2457 HR                                                                              O HR                                                                              2457 HR                                                                            Change                                                                             Initial                                                                           Final                      __________________________________________________________________________    NORMAL BAKE                                                                   A         93.2                                                                              99   92.9   99     -2.10                                                                             +7.7 9.8  0   0                          B         93.4                                                                              96   94.8   96     -2.21                                                                             +6.8 9.0  0   0                          C         93.0                                                                              88   90.5   88     -1.16                                                                             +12.0                                                                              13.2 0   2                          D         93.5                                                                              57   95.6   47     -1.77                                                                             +13.2                                                                              15.0 0   5                          E         93.3                                                                              62   92.1   62     -3.11                                                                             +13.5                                                                              16.6 0   4                          F         92.6                                                                               3   92.9    0     -3.3                                                                              +23.5                                                                              26.8 0   5                          OVERBAKE                                                                      G         97.6                                                                              94   93.6   62     +0.26                                                                             +9.2 8.9  0   0                          H         97.5                                                                              95   92.1   71     +0.02                                                                             +8.7 8.7  0   0                          I         97.1                                                                              78   86.3   43     +1.70                                                                             +14.5                                                                              12.8 0   3                          J         97.4                                                                              44   91.6   33     +0.78                                                                             +15.3                                                                              14.5 0   5                          K         96.4                                                                               6   90.8    0     -2.05                                                                             +19.7                                                                              21.8 0   5                          L         96.5                                                                               3   91.0    0     -2.75                                                                             +24.9                                                                              27.7 0   5                          __________________________________________________________________________

Although the present invention has been described with reference tocertain preferred embodiments, it is apparent that modifications andvariations thereof may be made by those skilled in the art withoutdeparting from the scope of this invention as defined by the appendedclaims.

We claim:
 1. A method of coating a substrate comprising the steps of (I)contacting said substrate with a curable composition comprising (i) astabilizingly effective amount of a stabilizer composition, (ii) acrosslinkingly effective amount of a crosslinking agent, and (iii) apolyfunctional active hydrogen containing material, and (II) thereaftercuring said curable composition, wherein the stabilizer compositioncomprises a monomeric or oligomeric aminoplast anchor having more than0.5 mole of phenolic light stabilizer groups per mole of aminoplastpendently attached thereto via an N-methylene bridge, represented by theformula ##STR108## wherein A is an m functional monomeric or oligomericaminoplast anchor molecule to which n phenolic light stabilizer groupsare attached through n N-methylene bridges, the bridges replacing theR², R³, R⁴ or R⁵ groups on the phenolic ring;R¹ is a group which,together with the phenolic ring, comprise the phenolic light stabilizergroup; R², R³, R⁴ and R⁵ are substituents independently selected fromthe group consisting of hydrogen, alkyl, aryl, aralkyl, hydroxy, alkoxy,and alkyl which is interrupted, substituted, or interrupted andsubstituted by one or more oxygen, carbonyl or carboxy groups;R⁶ ishydrogen or a blocking group selected from the group consisting ofalkyl, acyl, aminocarbonyl and silyl groups; m is at least 1; and n ismore than 0.5.
 2. The method as recited in claim 1, wherein theaminoplast anchor is selected from the group consisting of ##STR109##wherein R⁷ and R⁸ are independently selected from the group consistingof hydrogen, alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbonatoms, and aralkyl of 7 to 20 carbon atoms; andwhereinR⁹ is hydrogen ora linear or branched alkyl group of 1 to 20 carbon atoms; ##STR110##wherein R¹⁰ is selected from the group consisting of alkyl of 1 to 20carbon atoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20carbon atoms; and whereinR⁹ is hydrogen or a linear or branched alkylgroup of 1 to 20 carbon atoms; ##STR111## wherein R⁹ is hydrogen or alinear or branched alkyl group of 1 to 20 carbon atoms, and provided the(c) is not N-alkyl substituted; ##STR112## wherein R⁹ is hydrogen or alinear or branched alkyl group of 1 to 20 carbon atoms; ##STR113##wherein R⁹ is hydrogen or a linear or branched alkyl group of 1 to 20carbon atoms; ##STR114## wherein R⁹ is hydrogen or a linear or branchedalkyl group of 1 to 20 carbon atoms; ##STR115## wherein R⁹ is hydrogenor a linear or branched alkyl group of 1 to 20 carbon atoms; (h)oligomeric aminoplast anchor molecules derived from self- orcross-condensation of any of (a) through (g) and mixtures thereof; and(i) mixtures of any of (a) through (h).
 3. The method as recited inclaim 1, wherein the phenolic light stabilizer group is selected fromthe group consisting of 2-(2-hydroxyaryl)benzotriazoles,2-hydroxybenzophenones, 2-(2-hydroxyaryl)-4,6-diaryl-1,3,5-triazines,salicylic acid derivatives, 2-hydroxyoxanilides, blocked derivativesthereof, and mixtures of any of the preceding light stabilizer groups.4. The method as recited in claim 1, wherein A is attached through amethylene bridge replacing the R¹ or R⁵ group on the phenolic ring. 5.The method as recited in claim 1, wherein A is attached through amethylene bridge replacing the R³ group on the phenolic ring.
 6. Themethod as recited in claim 2, wherein the phenolic light stabilizergroup is selected from the group consisting of2-(2-hydroxyaryl)benzotriazoles, 2-hydroxybenzophenones,2-(2-hydroxyaryl)-4,6-diaryl-1,3,5-triazines, salicylic acidderivatives, 2-hydroxyoxanilides, blocked derivatives thereof, andmixtures of any of the preceding light stabilizer groups.
 7. The methodas recited in claim 2, wherein A is attached through a methylene bridgereplacing the R¹ or R⁵ group on the phenolic ring.
 8. The method asrecited in claim 2, wherein A is attached through a methylene bridgereplacing the R³ group on the phenolic ring.
 9. The method as recited inclaim 1, wherein the stabilizer composition comprises a monomeric oroligomeric aminoplast anchor having more than 0.5 mole of phenolic lightstabilizer group per mole of aminoplast pendently attached thereto,represented by the formula ##STR116## wherein A is an m functionalaminoplast anchor molecule to which n phenol rings are attached throughn methylene bridges, said bridges replacing the R³, R⁴ or R⁵ groups onthe phenolic ring, which aminoplast anchor molecule is selected from thegroup consisting of ##STR117## wherein R⁷ and R⁸ are independentlyselected from the group consisting of hydrogen, alkyl of 1 to 20 carbonatoms, aryl of 6 to 20 carbon atoms, and aralkyl of 7 to 20 carbonatoms, andwhereinR⁹ is hydrogen or a linear or branched alkyl group of 1to 20 carbon atoms; ##STR118## wherein R¹⁰ is selected from the groupconsisting of alkyl of 1 to 20 carbon atoms, aryl of 6 to 20 carbonatoms, and aralkyl of 7 to 20 carbon atoms, and whereinR⁹ is hydrogen ora linear or branched alkyl group of 1 to 20 carbon atoms; ##STR119##wherein R⁹ is hydrogen or a linear or branched alkyl group of 1 to 20carbon atoms, and provided the (c) is not N-alkyl substituted;##STR120## wherein R⁹ is hydrogen or a linear or branched alkyl group of1 to 20 carbon atoms; ##STR121## wherein R⁹ is hydrogen or a linear orbranched alkyl group of 1 to 20 carbon atoms; ##STR122## wherein R⁹ ishydrogen or a linear or branched alkyl group of 1 to 20 carbon atoms;##STR123## wherein R⁹ is hydrogen or a linear or branched alkyl group of1 to 20 carbon atoms; (h) oligomeric aminoplast anchor molecules derivedfrom self- or cross-condensation of any of (a) through (g) and mixturesthereof; and (i) mixtures of any of (a) through (h), wherein m is atleast 1, and wherein n is more than 0.5, and wherein R¹ is selected fromthe group consisting of: ##STR124## wherein each of R¹¹ through R¹⁴ isindependently selected from the group consisting of alkyl of 1 to 20carbon atoms, alkoxy of 1 to 20 carbon atoms, aralkyl of 7 to 20 carbonatoms, hydrogen, chloro, bromo, cyano and nitro groups; ##STR125##wherein each of R¹⁵ and R¹⁶ is independently selected from the groupconsisting of alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbonatoms, aralkyl of 7 to 20 carbon atoms, hydrogen, chloro, bromo, cyano,nitro and hydroxy groups; ##STR126## wherein Y and Z are the same ordifferent aromatic carbocyclic radicals, and wherein each of R¹⁷ throughR²² is independently selected from the group consisting of alkyl of 1 to20 carbon atoms, alkoxy of 1 to 20 carbon atoms, hydrogen, chloro,bromo, cyano and nitro groups; (m) carboxylic group or amides or estersthereof; ##STR127## wherein each of R²³ and R²⁴ is independentlyselected from the group consisting of alkyl of 1 to 20 carbon atoms,alkoxy of 1 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms,hydrogen, chloro, bromo, cyano and nitro groups; (o) mixtures of (j) to(n); and wherein R² is selected from the group consisting of hydrogen,alkyl of 1 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms;wherein R³ is selected from the group consisting of hydrogen, alkyl of 1to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, and alkyl of 1 to20 carbon atoms which is interrupted, substituted, or interrupted andsubstituted by one or more oxygen, carbonyl or carboxy groups; whereinR⁴ is selected from the group consisting of hydrogen, hydroxy, alkyl of1 to 20 carbon atoms, aralkyl of 7 to 20 carbon atoms, alkoxy of 1 to 20carbon atoms, and alkyl of 1 to 20 carbon atoms which is interrupted,substituted, or interrupted and substituted by one or more oxygen,carbonyl or carboxy groups; and wherein R⁵ is selected from the groupconsisting of hydrogen, alkyl of 1 to 20 carbon atoms, and aralkyl of 7to 20 carbon atoms.
 10. The method as recited in claim 9, wherein thestabilizer composition comprises a monomeric or oligomeric aminoplastanchor having more than 0.5 mole of phenolic light stabilizer group permole of aminoplast pendently attached thereto, represented by theformula ##STR128##
 11. The method as recited in claim 10, wherein theaminoplast anchor is a group of the formula ##STR129##
 12. The method asrecited in claim 10, wherein the aminoplast anchor is a group of theformula ##STR130##
 13. The method as recited in claim 10, wherein theaminoplast anchor is a group of the formula ##STR131##
 14. The method asrecited in claim 10, wherein the aminoplast anchor is a group of theformula ##STR132##
 15. The method as recited in claim 10, wherein A isattached through a methylene bridge replacing the R⁵ group on thephenolic ring.
 16. The method as recited in claim 10, wherein A isattached through a methylene bridge replacing the R³ group on thephenolic ring.
 17. The method as recited in claim 9, wherein thestabilizer composition comprises a monomeric or oligomeric aminoplastanchor having more than 0.5 mole of phenolic light stabilizer group permole of aminoplast pendently attached thereto, represented by theformula ##STR133##
 18. The method as recited in claim 17, wherein theaminoplast anchor is a group of the formula ##STR134##
 19. The method asrecited in claim 17, wherein the aminoplast anchor is a group of theformula ##STR135##
 20. The method as recited in claim 17, wherein theaminoplast anchor is a group of the formula ##STR136##
 21. The method asrecited in claim 17, wherein the aminoplast anchor is a group of theformula ##STR137##
 22. The method as recited in claim 17, wherein A isattached through a methylene bridge replacing the R⁵ group on thephenolic ring.
 23. The method as recited in claim 17, wherein A isattached through a methylene bridge replacing the R³ group on thephenolic ring.
 24. The method as recited in claim 9, wherein thestabilizer composition comprises a monomeric or oligomeric aminoplastanchor having more than 0.5 mole of phenolic light stabilizer group permole of aminoplast pendently attached thereto, represented by theformula ##STR138##
 25. The method as recited in claim 24, wherein theaminoplast anchor is a group of the formula ##STR139##
 26. The method asrecited in claim 24, wherein the aminoplast anchor is a group of theformula ##STR140##
 27. The method as recited in claim 24, wherein theaminoplast anchor is a group of the formula ##STR141##
 28. The method asrecited in claim 24, wherein the aminoplast anchor is a group of theformula ##STR142##
 29. The method as recited in claim 24, wherein A isattached through a methylene bridge replacing the R⁵ group on thephenolic ring.
 30. The method as recited in claim 24, wherein A isattached through a methylene bridge replacing the R³ group on thephenolic ring.
 31. The method as recited in claim 9, wherein thestabilizer composition comprises a monomeric or oligomeric aminoplastanchor having more than 0.5 mole of phenolic light stabilizer group permole of aminoplast pendently attached thereto, represented by theformula ##STR143##
 32. The method as recited in claim 31, wherein theaminoplast anchor is a group of the formula ##STR144##
 33. The method asrecited in claim 31, wherein the aminoplast anchor is a group of theformula ##STR145##
 34. The method as recited in claim 31, wherein theaminoplast anchor is a group of the formula ##STR146##
 35. The method asrecited in claim 31, wherein the aminoplast anchor is a group of theformula ##STR147##
 36. The method as recited in claim 31, wherein A isattached through a methylene bridge replacing the R⁵ group on thephenolic ring.
 37. The method as recited in claim 31, wherein A isattached through a methylene bridge replacing the R³ group on thephenolic ring.
 38. The method of claim 1, wherein the curablecomposition comprises (i) about 0.01 to 5 weight percent of thestabilizer composition, (ii) about 3 to 55 weight percent of thecrosslinking agent, and (iii) about 40 to 97 weight percent of thepolyfunctional active hydrogen containing material.
 39. The method ofclaim 9, wherein the curable composition comprises (i) about 0.01 to 5weight percent of the stabilizer composition, (ii) about 3 to 55 weightpercent of the crosslinking agent, and (iii) about 40 to 97 weightpercent of the polyfunctional active hydrogen containing material. 40.The method of claim 10, wherein the curable composition comprises (i)about 0.01 to 5 weight percent of the stabilizer composition, (ii) about3 to 55 weight percent of the crosslinking agent, and (iii) about 40 to97 weight percent of the polyfunctional active hydrogen containingmaterial.
 41. The method of claim 17, wherein the curable compositioncomprises (i) about 0.01 to 5 weight percent of the stabilizercomposition, (ii) about 3 to 55 weight percent of the crosslinkingagent, and (iii) about 40 to 97 weight percent of the polyfunctionalactive hydrogen containing material.
 42. The method of claim 24, whereinthe curable composition comprises (i) about 0.01 to 5 weight percent ofthe stabilizer composition, (ii) about 3 to 55 weight percent of thecrosslinking agent, and (iii) about 40 to 97 weight percent of thepolyfunctional active hydrogen containing material.
 43. The method ofclaim 31, wherein the curable composition comprises (i) about 0.01 to 5weight percent of the stabilizer composition, (ii) about 3 to 55 weightpercent of the crosslinking agent, and (iii) about 40 to 97 weightpercent of the polyfunctional active hydrogen containing material. 44.The method as recited in claim 1 wherein the crosslinking agent (ii) isan aminoplast resin selected from the group consisting of unetherifiedaminoplast resins, partially etherified aminoplast resins, fullyetherified aminoplast resins, and mixtures thereof.
 45. The method asrecited in claim 44 wherein the aminoplast crosslinking agent isselected from the group consisting of alkoxymethylated melamines,alkoxymethylated guanamines, alkoxymethylated glycolurils,alkoxymethylated ureas, oligomers thereof, and mixtures of any of thepreceding crosslinking agents.
 46. The method as recited in claim 1wherein the polyfunctional active hydrogen containing material (iii)comprises at least one class of active hydrogen functionality selectedfrom the group consisting of hydroxy, mercapto, amido, carboxy, and agroup convertible thereto.
 47. The method as recited in claim 46 whereinthe active hydrogen containing material (iii) is selected from the groupconsisting of acrylic resins, polyester resins, polyurethane polyols,products of condensation of amines with epoxy resins, polyols,polycarboxy compounds, polymercaptans, polyamides, and mixtures thereof.48. The method as recited in claim 1 further comprising a cure catalyst(iv).
 49. The method as recited in claim 48 wherein the cure catalyst isselected from the group consisting of sulfonic acids, carboxylic acids,phosphonic acids, sulfonimides, nitric acid, sulfuric acid, andphosphoric acid.
 50. The method as recited in claim 49 wherein the curecatalyst is selected from the group consisting of para-toluenesulfonicacid, benzenesulfonic acid, dinonylnaphthalenedisulfonic acid,naphthalenesulfonic acid, dodecylbenzenesulfonic acid, and methylpara-tolylsulfonimide.
 51. The method as recited in claim 50 wherein thecure catalyst is para-toluenesulfonic acid.
 52. The method as recited inclaim 1 wherein the substrate is selected from the group consisting ofsteel, aluminum, and plastic materials.
 53. The method as recited inclaim 1 wherein contacting is carried out by a method selected from thegroup consisting of spraying, padding, brushing, electrostatic spraying,roller coating, curtain coating, flow coating, dipping, andelectrocoating.
 54. The method as recited in claim 1 wherein the curingis carried out by continued application of heat.